EP3084765B1 - Holographic media with increased photosensitivity - Google Patents

Holographic media with increased photosensitivity Download PDF

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Publication number
EP3084765B1
EP3084765B1 EP14812248.4A EP14812248A EP3084765B1 EP 3084765 B1 EP3084765 B1 EP 3084765B1 EP 14812248 A EP14812248 A EP 14812248A EP 3084765 B1 EP3084765 B1 EP 3084765B1
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Prior art keywords
photopolymer
fluorine
chlorine
radicals
bromine
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EP14812248.4A
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German (de)
French (fr)
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EP3084765A1 (en
EP3084765B8 (en
Inventor
Thomas RÖLLE
Horst Berneth
Friedrich-Karl Bruder
Dennis Hönel
Thomas Fäcke
Günther WALZE
Rainer Hagen
Christian Diedrich
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Covestro Intellectual Property GmbH and Co KG
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Covestro Deutschland AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/001—Phase modulating patterns, e.g. refractive index patterns
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G03H2001/026—Recording materials or recording processes
    • G03H2001/0264—Organic recording material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2260/00—Recording materials or recording processes
    • G03H2260/12—Photopolymer
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/2403—Layers; Shape, structure or physical properties thereof
    • G11B7/24035—Recording layers
    • G11B7/24044—Recording layers for storing optical interference patterns, e.g. holograms; for storing data in three dimensions, e.g. volume storage

Definitions

  • the present invention relates to a photopolymer formulation comprising matrix polymers, a writing monomer and a photoinitiator.
  • the invention further relates to a photopolymer comprising matrix polymers, a writing monomer and a photoinitiator, a holographic medium which contains a photopolymer according to the invention, the use of a holographic medium according to the invention and a process for producing a holographic medium using a photopolymer formulation according to the invention.
  • Photopolymer formulations of the type mentioned at the outset are known in the prior art.
  • WO 2008/125229 A1 describes a photopolymer formulation and a photopolymer obtainable therefrom which comprise polyurethane matrix polymers, an acrylate-based writing monomer and photoinitiators containing a coinitiator and a dye.
  • the refractive index modulation ⁇ n produced by the holographic exposure plays a decisive role.
  • the interference field consisting of the signal and reference light beam (in the simplest case that of two plane waves) is imaged in a refractive index grating by the local photopolymerization of writing monomers such as highly refractive acrylates at locations of high intensity in the interference field.
  • the refractive index grating in the photopolymer contains all the information of the signal light beam.
  • the signal can then be reconstructed by illuminating the hologram only with the reference light beam.
  • the strength of the signal reconstructed in this way in relation to the strength of the incident reference light is called diffraction efficiency, hereinafter referred to as DE as diffraction efficiency.
  • the DE results from the quotient of the intensity of the light refracted during the reconstruction and the sum of the intensities from undeflected and refracted light.
  • the matrix polymers and the writing monomers of a photopolymer formulation should in principle be selected so that their refractive indices differ as much as possible.
  • One way of realizing this is to use matrix polymers with the lowest possible refractive index and writing monomers with the highest possible refractive index.
  • Suitable matrix polymers with a low refractive index are, for example, polyurethanes obtainable by reacting a polyol with a polyisocyanate component.
  • the matrix polymers are highly cross-linked in the finished medium. If the degree of crosslinking is too low, the medium is not sufficiently stable. This can result in the quality of holograms written in the media being considerably reduced. In the worst case, the holograms can even be destroyed afterwards.
  • holographic exposure with a continuous laser source reaches technical limits with large-area exposure, since a certain light dose per unit area must always be irradiated in order to ensure efficient formation of the hologram and the technically available laser power is limited.
  • large exposures with a comparatively low dose require long exposure times, which in turn place very high demands on the mechanical vibration damping of the exposure structure.
  • Typical pulse durations for pulsed lasers are 500 ns or shorter.
  • Typical pulse durations for continuous wave lasers with very fast shutters are 100 ⁇ s or shorter.
  • the same dose of energy can be irradiated as with continuous lasers in seconds. In this way, holograms can be written point by point. Since pulsed lasers or fast optical shutters are technically available and such an exposure structure has very low requirements with regard to mechanical vibration damping, it is a good technical alternative to the structures described above with continuous lasers for large-area exposure of holograms.
  • the object of the present invention was therefore to provide a photopolymer formulation which can be used to produce photopolymers in which holograms can be written using pulsed lasers due to their higher sensitivity to light.
  • media which are produced from a photopolymer formulation according to the invention have a higher sensitivity to light and are therefore well suited for exposure to pulsed lasers.
  • a 1 , A 2 and A 3 are each independently fluorine, chlorine, bromine or iodine and more preferably A 1 , A 2 and A 3 are either fluorine, chlorine, bromine or iodine at the same time.
  • R 1 , R 2 , R 3 , R 4 , R 5 in each case independently of one another, hydrogen, halogen, cyano, nitro, isonitrile, acyl, carboxyl, carbonate ester, carbonamide, orthoester, Sulfonate, phosphate, organosulfonyl, organosulfoxidyl, optionally fluorinated alkoxy and preferably hydrogen, halogen, cyano, nitro, isonitrile, acyl, carboxyl, are more preferably hydrogen, halogen and particularly preferably hydrogen, fluorine, chlorine, bromine or iodine.
  • the matrix polymers of the photopolymer formulation according to the invention can in particular be crosslinked and particularly preferably be three-dimensionally crosslinked.
  • the matrix polymers are polyurethanes, the polyurethanes being obtainable in particular by reacting at least one polyisocyanate component a) with at least one isocyanate-reactive component b)
  • the polyisocyanate component a) preferably comprises at least one organic compound with at least two NCO groups. These organic compounds can in particular be monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers.
  • the polyisocyanate component a) can also contain or consist of mixtures of monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers.
  • Monomeric di- and triisocyanates which can be used are all compounds known per se to those skilled in the art or mixtures thereof. These compounds can have aromatic, araliphatic, aliphatic or cycloaliphatic structures. In minor amounts, the monomeric di- and triisocyanates can also be monoisocyanates, i.e. include organic compounds with an NCO group.
  • Suitable monomeric di- and triisocyanates are 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 2,2,4-trimethylhexamethylene diisocyanate and / or 2,4,4-trimethylhexamethylene diisocyanate ( TMDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, bis (4,4'-isocyanatocyclohexyl) methane and / or bis- (2 ', 4-isocyanatocyclohexyl) methane and / or their mixtures of any isomer content, 1,4-cyclohexane diisocyanate, the isomeric bis- (isocyanatomethyl) cyclohexanes, 2,4- and / or 2,6-diis
  • Suitable polyisocyanates are compounds with urethane, urea, carbodiimide, acylurea, amide, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione and / or iminooxadiazinedione structures, which are obtainable from the aforementioned di- or triisocyanates.
  • the polyisocyanates are particularly preferably oligomerized aliphatic and / or cycloaliphatic di- or triisocyanates, it being possible in particular to use the above aliphatic and / or cycloaliphatic di- or triisocyanates.
  • Polyisocyanates with isocyanurate, uretdione and / or iminooxadiazinedione structures and biurets based on HDI or mixtures thereof are very particularly preferred.
  • Suitable prepolymers contain urethane and / or urea groups and, if appropriate, further structures formed by modifying NCO groups, as mentioned above.
  • Such prepolymers can be obtained, for example, by reacting the above-mentioned monomeric di- and triisocyanates and / or polyisocyanates a1) with isocyanate-reactive compounds b1).
  • Alcohols, amino or mercapto compounds, preferably alcohols, can be used as isocyanate-reactive compounds b1).
  • these can be polyols.
  • Polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane polyols can very particularly preferably be used as the isocyanate-reactive compound b1).
  • Suitable polyester polyols are, for example, linear polyester diols or branched polyester polyols which can be obtained in a known manner by reacting aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides with polyhydric alcohols having an OH functionality ⁇ 2.
  • suitable di- or polycarboxylic acids are polyvalent carboxylic acids such as succinic, adipic, cork, sebacic, decanedicarbonic, phthalic, terephthalic, isophthalic, tetrahydrophthalic or trimellitic acid and acid anhydrides such as phthalic, trimellitic or succinic anhydride or their arbitrary mixtures with each other.
  • the polyester polyols can also be based on natural raw materials such as castor oil. It is also possible that the polyester polyols are based on homopolymers or copolymers of lactones, preferably by adding lactones or lactone mixtures such as butyrolactone, ⁇ -caprolactone and / or methyl- ⁇ -caprolactone to hydroxy-functional compounds such as polyhydric alcohols with an OH functionality ⁇ 2 can be obtained for example of the type mentioned below.
  • suitable alcohols are all polyhydric alcohols, such as, for example, the C 2 -C 12 -diols, the isomeric cyclohexanediols, glycerol or any mixtures thereof with one another.
  • Suitable polycarbonate polyols can be obtained in a manner known per se by reacting organic carbonates or phosgene with diols or diol mixtures.
  • Suitable organic carbonates are dimethyl, diethyl and diphenyl carbonate.
  • Suitable diols or mixtures include the polyhydric alcohols mentioned per se in the context of the polyester segments with an OH functionality Rushzugt 2, preferably 1,4-butanediol, 1,6-hexanediol and / or 3-methylpentanediol. Polyester polyols can also be converted into polycarbonate polyols.
  • Suitable polyether polyols are polyadducts of cyclic ethers with OH- or NH-functional starter molecules which are optionally built up in blocks.
  • Suitable cyclic ethers are, for example, styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin and any mixtures thereof.
  • polyhydric alcohols having an OH functionality 2 2 which are mentioned per se in the context of the polyester polyols, and primary or secondary amines and amino alcohols can be used as starters.
  • Preferred polyether polyols are those of the aforementioned type exclusively based on propylene oxide or random or block copolymers based on propylene oxide with further 1-alkylene oxides.
  • Propylene oxide homopolymers and random or block copolymers which have oxyethylene, oxypropylene and / or oxybutylene units are particularly preferred, the proportion of oxypropylene units based on the total amount of all oxyethylene, oxypropylene and oxybutylene units being at least 20% by weight, preferably accounts for at least 45% by weight.
  • Oxypropylene and oxybutylene include all linear and branched C 3 and C 4 isomers.
  • components of the polyol component b1) as polyfunctional, isocyanate-reactive compounds are also low molecular weight, i.e. with molecular weights ⁇ 500 g / mol, short-chain, i.e. Aliphatic, araliphatic or cycloaliphatic di-, tri- or polyfunctional alcohols containing 2 to 20 carbon atoms are suitable.
  • triols examples include trimethylolethane, trimethylolpropane or glycerin.
  • Suitable higher-functional alcohols are di- (trimethylolpropane), pentaerythritol, dipentaerythritol or sorbitol.
  • the polyol component is a difunctional polyether, polyester or a polyether-polyester block copolyester or a polyether-polyester block copolymer with primary OH functions.
  • amines as the isocyanate-reactive compounds b1).
  • suitable amines are ethylene diamine, propylene diamine, diaminocyclohexane, 4,4'-dicylohexyl methane diamine, isophorone diamine (IPDA), difunctional polyamines such as e.g. the Jeffamine®, amine-terminated polymers, in particular with number-average molar masses ⁇ 10000 g / mol. Mixtures of the aforementioned amines can also be used.
  • amino alcohols as isocyanate-reactive compounds b1).
  • suitable amino alcohols are the isomeric aminoethanols, the isomeric aminopropanols, the isomeric aminobutanols and the isomeric aminohexanols or any mixtures thereof.
  • All of the aforementioned isocyanate-reactive compounds b1) can be mixed with one another as desired.
  • the isocyanate-reactive compounds b1) have a number-average molar mass of 200 200 and 100 10000 g / mol, more preferably 500 500 and 8 8000 g / mol and very particularly preferably 800 800 and 5000 5000 g / mol.
  • the OH functionality of the polyols is preferably 1.5 to 6.0, particularly preferably 1.8 to 4.0.
  • the prepolymers of polyisocyanate component a) can in particular have a residual free monomeric di- and triisocyanate content of ⁇ 1% by weight, particularly preferably ⁇ 0.5% by weight and very particularly preferably ⁇ 0.3% by weight.
  • the polyisocyanate component a) may contain all or part of the organic compound whose NCO groups have been reacted, in whole or in part, with blocking agents known from coating technology.
  • blocking agents are alcohols, lactams, oximes, malonic esters, pyrazoles and amines, such as e.g. Butanone oxime, diisopropylamine, diethyl malonate, acetoacetic ester, 3,5-dimethylpyrazole, ⁇ -caprolactam, or mixtures thereof.
  • the polyisocyanate component a) comprises compounds with aliphatically bound NCO groups, aliphatically bound NCO groups being understood to mean those groups which are bound to a primary carbon atom.
  • the isocyanate-reactive component b) preferably comprises at least one organic compound which has on average at least 1.5 and preferably 2 to 3 isocyanate-reactive groups. As part of the present Hydroxy, amino or mercapto groups are preferably regarded as isocyanate-reactive groups.
  • the isocyanate-reactive component can in particular comprise compounds which have a number average of at least 1.5 and preferably 2 to 3 isocyanate-reactive groups.
  • Suitable polyfunctional, isocyanate-reactive compounds of component b) are, for example, the compounds b1) described above.
  • the writing monomer c) comprises or consists of at least one mono- and / or a multifunctional writing monomer. More preferably, the writing monomer can comprise or consist of at least one mono- and / or a multifunctional (meth) acrylate writing monomer. The writing monomer can very particularly preferably comprise or consist of at least one mono- and / or a multifunctional urethane (meth) acrylate.
  • Suitable acrylate writing monomers are in particular compounds of the general formula (II) in which n ⁇ 1 and n ⁇ 4 and R 6 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted with heteroatoms organic radical and / or R 7 is hydrogen, a linear, branched, cyclic or heterocyclic unsubstituted or optionally also Heteroatoms substituted organic radical.
  • R 7 is particularly preferably hydrogen or methyl and / or R 6 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted with heteroatoms organic radical.
  • acrylates or methacrylates are esters of acrylic acid or methacrylic acid.
  • examples of acrylates and methacrylates which can be used with preference are phenyl acrylate, phenyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxyethoxyethyl acrylate, phenoxyethoxyethyl methacrylate, phenylthioethyl acrylate, phenylthioethyl methacrylate, 2-naphthylacrylate, 2-naphthyl-methyl-1,4-1,4-methacrylate, 1,4-butyl methacrylate - bis (2-thionaphthyl) -2-butyl methacrylate, Bisphenol A diacrylate, bisphenol A dimethacrylate, and their ethoxylated analog compounds, N-carbazolylacrylates.
  • urethane acrylates are understood to mean compounds with at least one acrylic ester group and at least one urethane bond. Such compounds can be obtained, for example, by reacting a hydroxy-functional acrylate or methacrylate with an isocyanate-functional compound.
  • isocyanate-functional compounds which can be used for this purpose are monoisocyanates and the monomeric diisocyanates, triisocyanates and / or polyisocyanates mentioned under a).
  • suitable monoisocyanates are phenyl isocyanate, the isomeric methylthiophenyl isocyanates.
  • Di-, tri- or polyisocyanates are mentioned above, as well as triphenylmethane-4,4 ', 4 "-triisocyanate and tris (p-isocyanatophenyl) thiophosphate or their derivatives with urethane, urea, carbodiimide, acylurea, isocyanurate, Allophanate, biuret, oxadiazinetrione, uretdione, iminooxadiazinedione structure and mixtures thereof, preference being given to aromatic di-, tri- or polyisocyanates.
  • Hydroxy-functional acrylates or methacrylates for the production of urethane acrylates include, for example, compounds such as 2-hydroxyethyl (meth) acrylate, polyethylene oxide mono- (meth) acrylates, polypropylene oxide mono (meth) acrylates, polyalkylene oxide mono (meth) acrylates, poly ( ⁇ -caprolactone) ) mono (meth) acrylates, such as Tone® M100 (Dow, Schwalbach, DE), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, hydroxypropyl (meth) acrylate, acrylic acid (2-hydroxy-3-phenoxypropyl ester), the hydroxy-functional mono-, di- or tetraacrylates of polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol
  • Urethane acrylates obtained from the reaction of tris (p-isocyanatophenyl) thiophosphate and / or m-methylthiophenyl isocyanate with alcohol-functional acrylates are particularly preferred such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and / or hydroxybutyl (meth) acrylate.
  • the writing monomer may contain further unsaturated compounds such as ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as maleinates, fumarates, maleimides, acrylamides, compounds containing vinyl ethers, propenyl ethers, allyl ethers and dicyclopentadienyl units as well as olefinically unsaturated compounds such as e.g. Styrene, ⁇ -methylstyrene, vinyltoluene and / or olefins, comprises or consists thereof.
  • unsaturated compounds such as ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as maleinates, fumarates, maleimides, acrylamides, compounds containing vinyl ethers, propenyl ethers, allyl ethers and dicyclopentadienyl units
  • olefinically unsaturated compounds such as e.g. Styrene, ⁇ -methylstyrene, vinyltol
  • Photoinitiators of component d) are usually compounds which can be activated by actinic radiation and can trigger polymerization of the writing monomers.
  • photoinitiators a distinction can be made between unimolecular (type I) and bimolecular (type II) initiators.
  • type I unimolecular
  • type II bimolecular
  • photoinitiators for radical, anionic, cationic or mixed types of polymerization.
  • Type I photoinitiators for radical photopolymerization form free radicals when irradiated by unimolecular bond cleavage.
  • type I photoinitiators are triazines, oximes, benzoin ethers, benzil ketals, bis-imidazoles, aroylphosphine oxides, sulfonium and iodonium salts.
  • Type II photoinitiators for radical polymerization consist of a dye as a sensitizer and a coinitiator and undergo a bimolecular reaction when irradiated with light adapted to the dye. First, the dye absorbs a photon and transfers energy to the coinitiator from an excited state. This releases the radicals that trigger polymerization by electron or proton transfer or direct hydrogen abstraction.
  • type II photoinitiators are preferably used.
  • Such photoinitiator systems are in principle in the EP 0 223 587 A described and preferably consist of a mixture of one or more dyes with ammonium alkylaryl borate (s).
  • Suitable dyes which form a type II photoinitiator together with an ammonium alkylaryl borate are those in US Pat WO 2012062655 described cationic dyes in combination with the anions just described there.
  • Cationic dyes are preferably understood to mean those of the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes, phenoxazine dyes, Phenothiazine dyes, tri (het) arylmethane dyes - in particular diamino and triamino (het) arylmethane dyes, mono-, di-, tri- and pentamethinecyanine dyes, hemicyanine dyes, externally cationic merocyanine dyes, externally cationic neutrocyanine Dyes, zero methine dyes - especially naphtholactam dyes, streptocyanin dyes.
  • Such dyes are for example in H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Azine Dyes, Wiley-VCH Verlag, 2008 , H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Methine Dyes and Pigments, Wiley-VCH Verlag, 2008 , T. Gessner, U. Mayer in Ullmann's Encyclopedia of Industrial Chemistry, Triarylmethane and Diarylmethane Dyes, Wiley-VCH Verlag, 2000 described.
  • cationic dyes are Astrazon Orange G, Basic Blue 3, Basic Orange 22, Basic Red 13, Basic Violet 7, Methylene Blue, New Methylene Blue, Azure A, 2,4-Diphenyl-6- (4-methoxyphenyl) pyrylium, Safranin O , Astraphloxin, brilliant green, crystal violet, ethyl violet and thionine.
  • Preferred anions are in particular C 8 to C 25 alkanesulfonate, preferably C 13 to C 25 alkanesulfonate, C 3 to C 18 perfluoroalkanesulfonate, C 4 to C 18 perfluoroalkanesulfonate which carries at least 3 hydrogen atoms in the alkyl chain, C 9 to C 25 alkanoate, C 9 to C 25 alkenoate, C 8 to C 25 alkyl sulfate, preferably C 13 to C 25 alkyl sulfate, C 8 to C 25 alkenyl sulfate, preferably C 13 to C 25 alkenyl sulfate, C 3 to C 18 perfluoroalkyl sulfate, C 4 to C 18 perfluoroalkyl sulfate which carries at least 3 hydrogen atoms in the alkyl chain, polyether sulfates based on at least 4 equivalents of ethylene oxide and / or 4 equivalents of propylene oxide
  • the anion A - of the dye has an AClogP in the range from 1 to 30, particularly preferably in the range from 1 to 12 and particularly preferably in the range from 1 to 6.5.
  • the AClogP is after J. Comput. Aid. Mol. Des. 2005, 19, 453; Virtual Computational Chemistry Laboratory, http://www.vcclab.org .
  • Suitable ammonium alkylaryl borates are, for example ( Cunningham et al., RadTech'98 North America UV / EB Conference Proceedings, Chicago, Apr. 19-22, 1998 ): Tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinapthylhexylborate, tetrabutylammonium tris (4-tert.butyl) phenylbutylborate, BASF tetrabutylammonium tris (3-fluorophenyl) 19, hexa- (60-hexylate), (26-hexylborate), tris (3-fluorophenyl) 19-, (26-fluorophenyl), tris (3-fluorophenyl) 19-, Basel, Switzerland), 1-methyl-3-octylimidazolium dipentyldip
  • photoinitiators can be advantageous to use mixtures of these photoinitiators.
  • the type and concentration of photoinitiator must be adapted in a manner known to the person skilled in the art. More information is, for example, in PKT Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3, 1991, SITA Technology, London, pp. 61 - 328 described.
  • the photoinitiator comprises a combination of dyes, the absorption spectra of which at least partially cover the spectral range from 400 to 800 nm, with at least one coinitiator matched to the dyes.
  • At least one photoinitiator suitable for a laser light color selected from blue, green and red is contained in the photopolymer formulation.
  • the photopolymer formulation contains a suitable photoinitiator for at least two laser light colors selected from blue, green and red.
  • the photopolymer formulation contains a suitable photoinitiator for each of the laser light colors blue, green and red.
  • the photopolymer formulation additionally contains urethanes as additives, it being possible for the urethanes to be substituted in particular with at least one fluorine atom.
  • the urethanes can preferably have the general formula (III) in which m ⁇ 1 and m ⁇ 8 and R 8 , R 9 and R 10 are linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted with heteroatoms, organic radicals and / or R 9 , R 10 are independently hydrogen, wherein preferably at least one of the radicals R 8 , R 9 , R 10 is substituted with at least one fluorine atom and particularly preferably R 8 is an organic radical with at least one fluorine atom.
  • R 9 is particularly preferably a linear, branched, cyclic or heterocyclic unsubstituted or optionally also organic radical substituted with heteroatoms such as fluorine.
  • the matrix polymers of the photopolymer according to the invention can in particular be cross-linked and particularly preferably three-dimensionally cross-linked.
  • the matrix polymers are polyurethanes, the polyurethanes being obtainable in particular by reacting at least one polyisocyanate component with at least one isocyanate-reactive component.
  • the invention also relates to a holographic medium, in particular in the form of a film, containing a photopolymer according to the invention or obtainable using a photopolymer formulation according to the invention.
  • a holographic medium in particular in the form of a film, containing a photopolymer according to the invention or obtainable using a photopolymer formulation according to the invention.
  • Another object of the invention is the use of a photopolymer formulation according to the invention for the production of holographic media.
  • holographic information is imprinted therein.
  • the holographic media according to the invention can be processed into holograms by appropriate exposure processes for optical applications in the entire visible and near UV range (300-800 nm).
  • Visual holograms include all holograms that can be recorded by methods known to those skilled in the art. These include in-line (Gabor) holograms, off-axis holograms, full-aperture transfer holograms, white-light transmission holograms ("rainbow holograms), Denisyukholograms, off-axis reflection holograms, edge-lit holograms and holographic stereograms. Denisyukholograms, transmission holograms.
  • Possible optical functions of the holograms that can be produced with the photopolymer formulations according to the invention correspond to the optical functions of light elements such as lenses, mirrors, deflecting mirrors, filters, diffusing screens, diffraction elements, diffusers, light guides, light guides (waveguides), projection screens and / or masks. Combinations of these optical functions can also be combined independently of one another in a hologram. These optical elements often show frequency selectivity, depending on how the holograms were exposed and what dimensions the hologram has.
  • the media according to the invention can also be used to produce holographic images or representations, for example for personal portraits, biometric representations in security documents, or generally images or image structures for advertising, security labels, brand protection, branding, labels, design elements, decorations, illustrations, trading cards , Pictures and the like as well as pictures which can represent digital data also in combination with the products shown above.
  • Holographic images can have the impression of a three-dimensional image, but they can also represent image sequences, short films or a number of different objects, depending on the angle from which (also moving) light source, etc. it is illuminated. Due to these diverse design possibilities, holograms, especially volume holograms, represent an attractive technical solution for the above-mentioned application.
  • the present invention therefore furthermore relates to the use of a holographic medium according to the invention for recording in-line, off-axis, full-aperture transfer, white light transmissions, Denisyuk, off-axis reflection or edge-lit holograms and holographic stereograms, in particular for Production of optical elements, pictures or picture representations.
  • the present invention furthermore also relates to a method for producing a holographic medium using a photopolymer formulation according to the invention.
  • the photopolymer formulations can be used in particular for the production of holographic media in the form of a film.
  • a layer of a material or composite material that is transparent to light in the visible spectral range (transmission greater than 85% in the wavelength range from 400 to 780 nm) is coated on one or both sides and, if appropriate, a cover layer is applied to the photopolymer layer or layers.
  • Preferred materials or material composites of the carrier are based on polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene, polypropylene, cellulose acetate, cellulose hydrate, cellulose nitrate, cycloolefin polymers, polystyrene, polyepoxide, polysulfone, cellulose triacetate (CTA), polyamide, polyvinyl chloride, polyamide, polyvinyl chloride, polyamide, polyvinyl chloride, polyamide, polyvinyl chloride, polyamide, polyvinyl chloride, polyamide, polyvinyl chloride or polydicyclopentadiene or mixtures thereof.
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PET polybutylene terephthalate
  • polyethylene polypropylene
  • cellulose acetate cellulose hydrate
  • cellulose nitrate cycloolefin polymers
  • polystyrene polyep
  • Composite materials can be film laminates or coextrudates.
  • Preferred material composites are duplex and triplex films constructed according to one of the schemes A / B, A / B / A or A / B / C.
  • PC / PET, PET / PC / PET and PC / TPU thermoplastic polyurethane are particularly preferred.
  • the materials or material composites of the carrier can be provided with one-sided or double-sided anti-adhesive, antistatic, hydrophobic or hydrophilized.
  • the modifications mentioned serve the purpose on the side facing the photopolymer layer so that the photopolymer layer can be detached from the support without destruction.
  • a modification of the side of the support facing away from the photopolymer layer serves to ensure that the media according to the invention meet special mechanical requirements, which e.g. when processing in roll laminators, especially in roll-to-roll processes.
  • the Denisyuk hologram of a mirror was recorded in a sample consisting of a glass plate with a laminated photopolymer film.
  • the substrate of the photopolymer film pointed to the laser source and the glass substrate to the mirror.
  • the sample was aligned with its flat surface perpendicular to the laser beam. The distance between sample and mirror was 3 cm.
  • the wave plate allowed the rotation of the plane of polarization of the laser light and with the following polarizer the S-polarized portion of the laser light was reflected in the direction of the sample.
  • the beam expansion allowed the setting of the exposed area. The wave plate and beam expansion were adjusted so that the sample reached an exposure dose of 100 mJ / cm 2 / pulse.
  • the samples were each exposed precisely with a pulse. After exposure, the sample was bleached on a light table.
  • a transmission spectrum was measured through the hologram of the bleached sample.
  • a spectrometer from the company Ocean Optics, model HR4000 was used. The sample was placed perpendicular to the light beam.
  • the transmission spectrum showed a drop in transmission at the wavelength at which the Bragg condition was met.
  • the depth of the transmission dip to the baseline was evaluated as the diffraction efficiency DE of the Denisyuk hologram of the mirror.
  • Fomrez UL 28 Urethanization catalyst commercial product of Momentive Performance Chemicals, Wilton, CT, USA.
  • Aluminum chloride [7446-70-0] is available from Acros Organics, Geel, BE.
  • 1-chloro-3,4-difluorobenzene [696-02-6] is available from ABCR GmbH & CO. KG, Düsseldorf available.
  • 1-bromo-3,4-difluorobenzene [348-61-8] is available from ABCR GmbH & CO. KG, Düsseldorf available.
  • 1,4-difluorobenzene [540-36-3] is available from Aldrich Chemie, Steinheim.
  • 4-chlorofluorobenzene [352-33-0] is at ABCR GmbH & CO. KG, Düsseldorf available.
  • 4-bromofluorobenzene [460-00-4] is available from Aldrich Chemie, Steinheim.
  • 4-chlorophenyl magnesium bromide [873-77-8] is available as a 0.9 M solution in THF / toluene from Aldrich Chemie, Steinheim.
  • 4-fluorophenyl magnesium bromide [352-13-6] is available as a 1.0M solution in THF from Aldrich Chemie, Steinheim.
  • Tetrabutylammonium bromide [1643-19-2] is at ABCR GmbH & CO. KG, Düsseldorf available.
  • Safranin O [10309-89-4] is available from Chemos GmbH, Germany, item no. 1308 available.
  • the composition of the mixture of substances is in EP 2450893 A1 described.
  • Sodium bis (2-ethylhexyl) sulfosuccinate [45297-26-5] is available from Aldrich Chemie, Steinheim.
  • 4-fluorotrichlorobenzene [402-42-6] is available from ABCR GmbH & CO. KG, Düsseldorf available and was used as received.
  • the organic phase was washed once with 100 mL water, once with 100 mL 5% NaHCO 3 solution and once again with 100 mL water.
  • the carbon tetrachloride was distilled off and the desired product (5.6 g) crystallized from the oil in the form of colorless fine needles.
  • the organic phase was washed once with 100 mL water, once with 100 mL 5% NaHCO 3 solution and once again with 100 mL water.
  • the carbon tetrachloride was distilled off and a little acetonitrile was added.
  • the desired product (6.0 g) crystallized from this solution in the form of colorless fine needles.
  • the organic phase was washed once with 100 mL water, once with 100 mL 5% NaHCO 3 solution and once again with 100 mL water.
  • the carbon tetrachloride was distilled off and a little acetonitrile was added.
  • the desired product (8.0 g) crystallized from this solution in the form of colorless fine needles.
  • Example 8 Preparation of 1-chloro-4-fluoro-2- (trichloromethyl) benzene and 4-chloro-1-fluoro-2- (trichloromethyl) benzene :
  • additive 1 bis (2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) - (2,2,4-trimethylhexane-1,6-diyl) biscarbamate
  • TMDI 2,4,4-trimethylhexane-1,6-diisocyanate
  • borate 1 photoinitiator: tetrabutylammonium tris (4-chlorophenyl) (hexyl) borate
  • borate 2 photoinitiator: tetrabutylammonium tris (4-fluorophenyl) (hexyl) borate
  • Example Medium I The procedure was as in Example Medium I, but using 0.10 g borate 2 instead of 0.10 g borate 1.
  • Example Medium I The procedure was as in Example Medium I, but using 0.010 g of Example 2 instead of 0.010 g of Example 1.
  • Example Medium I The procedure was as in Example Medium I, but using 0.010 g of Example 3 instead of 0.010 g of Example 1 and using 0.10 g of Borate 2 instead of 0.10 g of Borate 1.
  • Example Medium I The procedure was as in Example Medium I, but using 0.010 g of Example 4 instead of 0.010 g of Example 1.
  • Example Medium I The procedure was as in Example Medium I, but using 0.010 g of Example 5 instead of 0.010 g of Example 1.
  • Example Medium I The procedure was as in Example Medium I, but using 0.010 g of Example 6 instead of 0.010 g of Example 1.
  • Example Medium I The procedure was as in Example Medium I, but using 0.010 g of Example 7 instead of 0.010 g of Example 1 and using 0.10 g of Borate 2 instead of 0.10 g of Borate 1.
  • Example Medium I The procedure was as in Example Medium I, but using 0.010 g of Example 8 instead of 0.010 g of Example 1 and using 0.10 g of Borate 2 instead of 0.10 g of Borate 1.
  • Example Medium I The procedure was as in Example Medium I, but using 0.010 g Example 9 instead of 0.010 g Example 1.
  • Example medium Example according to formula (I) Borate Single pulse DE [%] I. 1 1 22 II 1 2nd 21 III 2nd 1 38 IV 3rd 2nd 37 V 4th 1 29 VI 5 1 34 VII 6 1 19th VIII 7 2nd 24th IX 8th 2nd 26 X 9 1 27 Comparison medium Additive Borate Single pulse DE [%] V-1 - 1 - V-2 - 2nd -
  • the values found for the example media I to X show that the compounds of the formula (I) according to the invention used in the photopolymer formulations are very well suited for use in holographic media when exposed to a pulsed laser.
  • the comparison media V-1 and V-2 have no compound of the formula (I) according to the invention and are unsuitable for use in holographic media when exposed to a pulsed laser.

Description

Die vorliegende Erfindung betrifft eine Photopolymer-Formulierung umfassend Matrixpolymere, ein Schreibmonomer und einen Photoinitiator. Weitere Gegenstände der Erfindung sind ein Photopolymer umfassend Matrixpolymere, ein Schreibmonomer und einen Photoinitiator, ein holographisches Medium, das ein erfindungsgemäßes Photopolymer enthält, die Verwendung eines erfindungsgemäßen holographischen Mediums sowie ein Verfahren zur Herstellung eines holographischen Mediums unter Verwendung einer erfindungsgemäßen Photopolymer-Formulierung.The present invention relates to a photopolymer formulation comprising matrix polymers, a writing monomer and a photoinitiator. The invention further relates to a photopolymer comprising matrix polymers, a writing monomer and a photoinitiator, a holographic medium which contains a photopolymer according to the invention, the use of a holographic medium according to the invention and a process for producing a holographic medium using a photopolymer formulation according to the invention.

Photopolymer-Formulierungen der eingangs genannten Art sind im Stand der Technik bekannt. So sind beispielsweise in der WO 2008/125229 A1 eine Photopolymer-Formulierung und ein daraus erhältliches Photopolymer beschrieben, die Polyurethanmatrixpolymere, ein Schreibmonomer auf Acrylatbasis sowie Photoinitiatoren enthaltend einen Coinitiator und einen Farbstoff umfassen. Bei der Verwendungen von Photopolymeren spielt die durch die holographische Belichtung erzeugte Brechungsindexmodulation Δn die entscheidende Rolle. Bei der holographischen Belichtung wird das Interferenzfeld aus Signal- und Referenzlichtstrahl (im einfachsten Fall das zweier ebener Wellen) durch die lokale Photopolymerisation von Schreibmonomeren wie z.B. hochbrechenden Acrylate an Orten hoher Intensität im Interferenzfeld in ein Brechungsindexgitter abgebildet. Das Brechungsindexgitter im Photopolymer (das Hologramm) enthält alle Information des Signallichtstrahls. Durch Beleuchtung des Hologramms nur mit dem Referenzlichtstrahl kann dann das Signal wieder rekonstruiert werden. Die Stärke des so rekonstruierten Signals im Verhältnis zur Stärke des eingestrahlten Referenzlichts wird Beugungseffizienz, im Folgenden DE wie Diffraction Efficiency, genannt.Photopolymer formulations of the type mentioned at the outset are known in the prior art. For example, in the WO 2008/125229 A1 describes a photopolymer formulation and a photopolymer obtainable therefrom which comprise polyurethane matrix polymers, an acrylate-based writing monomer and photoinitiators containing a coinitiator and a dye. When using photopolymers, the refractive index modulation Δn produced by the holographic exposure plays a decisive role. In holographic exposure, the interference field consisting of the signal and reference light beam (in the simplest case that of two plane waves) is imaged in a refractive index grating by the local photopolymerization of writing monomers such as highly refractive acrylates at locations of high intensity in the interference field. The refractive index grating in the photopolymer (the hologram) contains all the information of the signal light beam. The signal can then be reconstructed by illuminating the hologram only with the reference light beam. The strength of the signal reconstructed in this way in relation to the strength of the incident reference light is called diffraction efficiency, hereinafter referred to as DE as diffraction efficiency.

Im einfachsten Fall eines Hologramms, das aus der Überlagerung zweier ebener Wellen entsteht, ergibt sich die DE aus dem Quotienten der Intensität des bei der Rekonstruktion abgebeugten Lichtes und der Summe der Intensitäten aus nicht gebeugten und abgebeugtem Licht. Je höher die DE desto effizienter ist ein Hologramm in Bezug auf die Lichtmenge des Referenzlichtes die notwendig ist, um das Signal mit einer festen Helligkeit sichtbar zu machen.In the simplest case of a hologram that arises from the superimposition of two plane waves, the DE results from the quotient of the intensity of the light refracted during the reconstruction and the sum of the intensities from undeflected and refracted light. The higher the DE, the more efficient a hologram is in relation to the amount of light of the reference light that is necessary to make the signal visible with a fixed brightness.

Um ein möglichst hohes Δn und eine möglichst hohe DE bei Hologrammen realisieren zu können, sollten grundsätzlich die Matrixpolymere und die Schreibmonomere einer Photopolymer-Formulierung so gewählt werden, dass sie sich in ihren Brechungsindizes möglichst stark unterscheiden. Ein Möglichkeit zur Realisierung ist, Matrixpolymere mit einem möglichst niedrigen und Schreibmonomere mit einem möglichst hohen Brechungsindex zu verwenden. Geeignete Matrixpolymere mit niedrigem Brechungsindex sind beispielsweise durch Umsetzung einer Polyol- mit einer Polyisocyanat-Komponente erhältliche Polyurethane.In order to be able to achieve the highest possible Δn and the highest possible DE for holograms, the matrix polymers and the writing monomers of a photopolymer formulation should in principle be selected so that their refractive indices differ as much as possible. One way of realizing this is to use matrix polymers with the lowest possible refractive index and writing monomers with the highest possible refractive index. Suitable matrix polymers with a low refractive index are, for example, polyurethanes obtainable by reacting a polyol with a polyisocyanate component.

Neben hohen DE- und Δn- Werten ist es für holographische Medien aus Photopolymer-Formulierungen aber auch von großer Bedeutung, dass die Matrixpolymere im fertigen Medium hoch vernetzt sind. Falls der Vernetzungsgrad zu niedrig ist, weist das Medium keine ausreichende Stabilität auf. Dies kann dazu führen, dass die Qualität von in die Medien eingeschriebenen Hologrammen erheblich vermindert ist. Im schlimmsten Fall können die Hologramme sogar nachträglich zerstört werden.In addition to high DE and Δn values, it is also very important for holographic media made from photopolymer formulations that the matrix polymers are highly cross-linked in the finished medium. If the degree of crosslinking is too low, the medium is not sufficiently stable. This can result in the quality of holograms written in the media being considerably reduced. In the worst case, the holograms can even be destroyed afterwards.

Weiterhin ist es insbesondere für den großtechnischen Einsatz von holographischen Medien aus Photopolymer-Formulierungen von großer Bedeutung, dass die Lichtempfindlichkeit ausreicht, um bei einer gegebenen Laser-Lichtquelle großflächig und ohne Verlust an Indexmodulation belichten zu können. Hier ist insbesondere die Wahl eines geeigneten Photoinitiators von entscheidender Bedeutung für die Eigenschaften des Photopolymers.Furthermore, it is of great importance, in particular for the large-scale use of holographic media made from photopolymer formulations, that the light sensitivity is sufficient to be able to expose a large area of a given laser light source without loss of index modulation. Here, the choice of a suitable photoinitiator is of crucial importance for the properties of the photopolymer.

Die holographische Belichtung mit einer kontinuierlichen Laserquelle stößt jedoch bei großflächiger Belichtung an technische Grenzen, da immer eine gewisse Lichtdosis pro Flächeneinheit eingestrahlt werden muss, um eine effiziente Bildung des Hologramms zu gewährleisten und die technisch verfügbare Laserleistung begrenzt ist. Zudem erfordern großflächige Belichtungen bei vergleichsweise geringer Dosis lange Belichtungszeiten, die wiederum sehr hohe Anforderungen an die mechanische Schwingungsdämpfung des Belichtungsaufbaus stellen.However, holographic exposure with a continuous laser source reaches technical limits with large-area exposure, since a certain light dose per unit area must always be irradiated in order to ensure efficient formation of the hologram and the technically available laser power is limited. In addition, large exposures with a comparatively low dose require long exposure times, which in turn place very high demands on the mechanical vibration damping of the exposure structure.

Eine weitere Möglichkeit zur großflächigen Belichtung von Hologrammen besteht in der Verwendung von sehr kurzen Lichtpulsen, wie sie z.B. von gepulsten Lasern oder Dauerstrichlasern in Verbindung mit sehr schnellen Shuttern erzeugt werden. Typische Pulsdauern bei gepulsten Lasern sind 500 ns oder kürzer. Typische Pulsdauern bei Dauerstrichlasern mit sehr schnellen Shuttern sind 100 µs oder kürzer. Dabei kann die gleiche Energiedosis eingestrahlt werden wie mit kontinuierlichen Lasern in Sekunden. Auf diese Art können Hologramme Punkt für Punkt geschrieben werden. Da gepulste Laser oder schnelle optische Shutter technisch verfügbar sind und ein derartiger Belichtungsaufbau sehr geringe Anforderungen mit Hinblick auf die mechanische Schwingungsdämpfung hat, handelt es sich um eine gute technisch Alternative zu den oben beschriebenen Aufbauten mit kontinuierlichen Lasern zur großflächigen Belichtung von Hologrammen.Another possibility for exposing holograms over a large area is to use very short light pulses, such as those e.g. of pulsed lasers or continuous wave lasers in connection with very fast shutters. Typical pulse durations for pulsed lasers are 500 ns or shorter. Typical pulse durations for continuous wave lasers with very fast shutters are 100 µs or shorter. The same dose of energy can be irradiated as with continuous lasers in seconds. In this way, holograms can be written point by point. Since pulsed lasers or fast optical shutters are technically available and such an exposure structure has very low requirements with regard to mechanical vibration damping, it is a good technical alternative to the structures described above with continuous lasers for large-area exposure of holograms.

Die aus der WO 2008/125229 A1 bekannten Photopolymere weisen auf Grund der dort verwendeten Photoinitiatoren eine zu geringe Lichtempfindlichkeit auf, um sie beim Schreiben von Hologrammen mit gepulsten Lasern verwenden zu können. Weitere Photopolymer-Formulierungen die Matrixpolymere, Schreibmonomere und Photoinitiatoren enthalten sind aus der WO 2013/053771 A und der WO 2011/095442 A1 bekannt.The one from the WO 2008/125229 A1 Known photopolymers have, due to the photoinitiators used there, too little light sensitivity to be able to use them when writing holograms with pulsed lasers. Further photopolymer formulations containing matrix polymers, writing monomers and photoinitiators are from the WO 2013/053771 A and the WO 2011/095442 A1 known.

Die Aufgabe der vorliegenden Erfindung bestand daher darin, eine Photopolymer-Formulierung bereit zu stellen, mit deren Hilfe sich Photopolymere herstellen lassen, in die auf Grund ihrer höheren Lichtempfindlichkeit mit gepulsten Lasern Hologramme geschrieben werden können.The object of the present invention was therefore to provide a photopolymer formulation which can be used to produce photopolymers in which holograms can be written using pulsed lasers due to their higher sensitivity to light.

Diese Aufgabe ist durch eine Photopolymer-Formulierung umfassend Matrixpolymere, ein Schreibmonomer und einen Photoinitiator gelöst, die zusätzlich eine Verbindung der Formel (I) umfasst

Figure imgb0001
worin

A1, A2, A3
jeweils unabhängig voneinander Wasserstoff, Fluor, Chlor, Brom oder Iod,
R1, R2, R3, R4, R5
jeweils unabhängig voneinander Wasserstoff, Halogen, Cyano, Nitro, Amino, Alkylimino, Azid, Isonitril, Enamino, Formyl, Acyl, Carboxyl, Carbonester, Carbonamid, Orthoester, Sulfonat, Phosphat, Organosulfonyl, Organo-sulfoxidyl, gegebenenfalls fluoriertes Alkoxy oder ein gegebenenfalls substituierter aromatischer, heteroaromatischer, aliphatischer, araliphatischer, olefinischer oder acetylenischer Rest sind und geeignete Reste über eine Brücke beliebiger Substitution miteinander verbunden sein können oder dass zwei oder mehrere Verbindungen der Formel (I) über mindestens einen der Reste R1, R2, R3, R4, R5 verbunden sein können, wobei diese Reste dann eine 2 - 4-fach funktionelle Brücke darstellen können, mit der Maßgabe, dass wenigstens einer der Reste R1, R2, R3, R4, R5 nicht Wasserstoff ist.
This object is achieved by a photopolymer formulation comprising matrix polymers, a writing monomer and a photoinitiator, which additionally comprises a compound of the formula (I)
Figure imgb0001
 wherein
A 1 , A 2 , A 3
each independently of one another hydrogen, fluorine, chlorine, bromine or iodine,
R 1 , R 2 , R 3 , R 4 , R 5
each independently of one another hydrogen, halogen, cyano, nitro, amino, alkylimino, azide, isonitrile, enamino, formyl, acyl, carboxyl, carbonate ester, carbonamide, orthoester, sulfonate, phosphate, organosulfonyl, organosulfoxidyl, optionally fluorinated alkoxy or an optionally substituted one aromatic, heteroaromatic, aliphatic, araliphatic, olefinic or acetylenic radical and suitable radicals can be connected to one another via a bridge of any substitution or that two or more compounds of the formula (I) have at least one of the radicals R 1 , R 2 , R 3 , R 4 , R 5 can be connected, these radicals then being able to represent a 2-4-fold functional bridge, with the proviso that at least one of the radicals R 1 , R 2 , R 3 , R 4 , R 5 is not hydrogen .

So wurde überraschenderweise gefunden, dass Medien, die aus einer erfindungsgemäßen Photopolymer-Formulierung hergestellt sind, eine höhere Lichtempfindlichkeit aufweisen und damit gut zur Belichtung mit gepulsten Lasern geeignet sind.It has surprisingly been found that media which are produced from a photopolymer formulation according to the invention have a higher sensitivity to light and are therefore well suited for exposure to pulsed lasers.

Gemäß einer bevorzugten Ausführungsform der erfindungsgemäßen Photopolymer-Formulierung ist vorgesehen, dass bei der Verbindung der Formel (I) A1, A2 und A3 jeweils unabhängig voneinander Fluor, Chlor, Brom oder Iod und weiter bevorzugt A1, A2 und A3 gleichzeitig entweder Fluor, Chlor, Brom oder Iod sind.According to a preferred embodiment of the photopolymer formulation according to the invention it is provided that in the compound of the formula (I) A 1 , A 2 and A 3 are each independently fluorine, chlorine, bromine or iodine and more preferably A 1 , A 2 and A 3 are either fluorine, chlorine, bromine or iodine at the same time.

Ebenfalls bevorzugt ist, wenn bei der Verbindung der Formel (I) R1, R2, R3, R4, R5 jeweils unabhängig voneinander Wasserstoff, Halogen, Cyano, Nitro, Isonitril, Acyl, Carboxyl, Carbonester, Carbonamid, Orthoester, Sulfonat, Phosphat, Organo-sulfonyl, Organo-sulfoxidyl, gegebenenfalls fluoriertes Alkoxy und bevorzugt Wasserstoff, Halogen, Cyano, Nitro, Isonitril, Acyl, Carboxyl, weiter bevorzugt Wasserstoff, Halogen und besonders bevorzugt Wasserstoff, Fluor, Chlor, Brom oder Iod sind.It is also preferred if, in the case of the compound of the formula (I) R 1 , R 2 , R 3 , R 4 , R 5, in each case independently of one another, hydrogen, halogen, cyano, nitro, isonitrile, acyl, carboxyl, carbonate ester, carbonamide, orthoester, Sulfonate, phosphate, organosulfonyl, organosulfoxidyl, optionally fluorinated alkoxy and preferably hydrogen, halogen, cyano, nitro, isonitrile, acyl, carboxyl, are more preferably hydrogen, halogen and particularly preferably hydrogen, fluorine, chlorine, bromine or iodine.

Die Matrixpolymere der erfindungsgemäßen Photopolymer-Formulierung können insbesondere vernetzt und besonders bevorzugt dreidimensional vernetzt sein.The matrix polymers of the photopolymer formulation according to the invention can in particular be crosslinked and particularly preferably be three-dimensionally crosslinked.

Vorteilhaft ist auch, wenn die Matrixpolymere Polyurethane sind, wobei die die Polyurethane insbesondere durch Umsetzung wenigstens einer Polyisocyanat-Komponente a) mit wenigstens einer Isocyanat-reaktiven-Komponente b) erhältlich sein könnenIt is also advantageous if the matrix polymers are polyurethanes, the polyurethanes being obtainable in particular by reacting at least one polyisocyanate component a) with at least one isocyanate-reactive component b)

Die Polyisocyanat-Komponente a) umfasst bevorzugt wenigstens eine organische Verbindung mit wenigstens zwei NCO-Gruppen. Bei diesen organischen Verbindungen kann es sich insbesondere um monomere Di- und Triisocyanate, Polyisocyanate und / oder NCO-funktionelle Prepolymere handeln. Die Polyisocyanat-Komponente a) kann auch Mischungen monomerer Di- und Triisocyanate, Polyisocyanate und / oder NCO-funktioneller Prepolymere enthalten oder daraus bestehen.The polyisocyanate component a) preferably comprises at least one organic compound with at least two NCO groups. These organic compounds can in particular be monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers. The polyisocyanate component a) can also contain or consist of mixtures of monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers.

Als monomere Di- und Triisocyanate können alle dem Fachmann an sich gut bekannten Verbindungen oder deren Mischungen eingesetzt werden. Diese Verbindungen können aromatische, araliphatische, aliphatische oder cycloaliphatische Strukturen aufweisen. In untergeordneten Mengen können die monomeren Di- und Triisocyanate auch Monoisocyanate, d.h. organische Verbindungen mit einer NCO-Gruppe umfassen.Monomeric di- and triisocyanates which can be used are all compounds known per se to those skilled in the art or mixtures thereof. These compounds can have aromatic, araliphatic, aliphatic or cycloaliphatic structures. In minor amounts, the monomeric di- and triisocyanates can also be monoisocyanates, i.e. include organic compounds with an NCO group.

Beispiele für geeignete monomere Di- und Triisocyanate sind 1,4-Butandiisocyanat, 1,5-Pentandiisocyanat, 1,6-Hexandiisocyanat (Hexamethylendiisocyanat, HDI), 2,2,4-Trimethylhexamethylendiisocyanat und / oder 2,4,4-Trimethylhexamethylendiisocyanat (TMDI), Isophorondiisocyanat (IPDI), 1,8-Diisocyanato-4-(isocyanatomethyl)-octan, Bis-(4,4'-isocyanatocyclohexyl)methan und / oder Bis-(2',4-isocyanatocyclohexyl)methan und / oder deren Mischungen beliebigen Isomerengehalts, 1,4-Cyclohexandiisocyanat, die isomeren Bis-(isocyanatomethyl)cyclohexane, 2,4- und / oder 2,6-Diisocyanato-1-methylcyclohexan (Hexahydro-2,4- und / oder 2,6-toluylendiisocyanat, H6-TDI), 1,4-Phenylendiisocyanat, 2,4- und / oder 2,6-Toluylendiisocyanat (TDI), 1,5-Naphthylendiisocyanat (NDI), 2,4'- und / oder 4,4'-Diphenylmethandiisocyanat (MDI), 1,3-Bis-(isocyanatomethyl)benzol (XDI) und / oder das analoge 1,4-Isomere oder beliebige Mischungen der vorgenannten Verbindungen.Examples of suitable monomeric di- and triisocyanates are 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 2,2,4-trimethylhexamethylene diisocyanate and / or 2,4,4-trimethylhexamethylene diisocyanate ( TMDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, bis (4,4'-isocyanatocyclohexyl) methane and / or bis- (2 ', 4-isocyanatocyclohexyl) methane and / or their mixtures of any isomer content, 1,4-cyclohexane diisocyanate, the isomeric bis- (isocyanatomethyl) cyclohexanes, 2,4- and / or 2,6-diisocyanato-1-methylcyclohexane (hexahydro-2,4- and / or 2,6- tolylene diisocyanate, H 6 -TDI), 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 1,5-naphthylene diisocyanate (NDI), 2,4'- and / or 4,4 '-Diphenylmethane diisocyanate (MDI), 1,3-bis (isocyanatomethyl) benzene (XDI) and / or the analogous 1,4-isomer or any mixtures of the aforementioned compounds.

Geeignete Polyisocyanate sind Verbindungen mit Urethan-, Harnstoff-, Carbodiimid-, Acylharnstoff-, Amid-, Isocyanurat-, Allophanat-, Biuret-, Oxadiazintrion-, Uretdion- und/oder Iminooxadiazindionstrukturen, die aus den vorgenannten Di- oder Triisocyanaten erhältlich sind.Suitable polyisocyanates are compounds with urethane, urea, carbodiimide, acylurea, amide, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione and / or iminooxadiazinedione structures, which are obtainable from the aforementioned di- or triisocyanates.

Besonders bevorzugt handelt es sich bei den Polyisocyanaten um oligomerisierte aliphatische und / oder cycloaliphatische Di- oder Triisocyanate, wobei insbesondere die oben stehenden aliphatischen und / oder cycloaliphatischen Di- oder Triisocyanate verwendet werden können.The polyisocyanates are particularly preferably oligomerized aliphatic and / or cycloaliphatic di- or triisocyanates, it being possible in particular to use the above aliphatic and / or cycloaliphatic di- or triisocyanates.

Ganz besonders bevorzugt sind Polyisocyanate mit Isocyanurat-, Uretdion- und / oder Iminooxadiazindion-Strukturen sowie Biurete basierend auf HDI oder deren Mischungen.Polyisocyanates with isocyanurate, uretdione and / or iminooxadiazinedione structures and biurets based on HDI or mixtures thereof are very particularly preferred.

Geeignete Prepolymere enthalten Urethan- und / oder Harnstoff-Gruppen sowie gegebenenfalls weitere durch Modifizierung von NCO-Gruppen entstandene Strukturen wie oben genannt. Derartige Prepolymere sind beispielsweise durch Umsetzung der oben genannten monomeren Di- und Triisocyanate und / oder Polyisocyanaten a1) mit isocyanatreaktiven Verbindungen b1) erhältlich.Suitable prepolymers contain urethane and / or urea groups and, if appropriate, further structures formed by modifying NCO groups, as mentioned above. Such prepolymers can be obtained, for example, by reacting the above-mentioned monomeric di- and triisocyanates and / or polyisocyanates a1) with isocyanate-reactive compounds b1).

Als isocyanatreaktive Verbindungen b1) können Alkohole, Amino oder Mercapto-Verbindungen, bevorzugt Alkohole, verwendet werden. Dabei kann es sich insbesondere um Polyole handeln. Ganz besonders bevorzugt können als isocyanatreaktive Verbindung b1) Polyester-, Polyether-, Polycarbonat-, Poly(meth)acrylat- und/oder Polyurethan-Polyole verwendet werden.Alcohols, amino or mercapto compounds, preferably alcohols, can be used as isocyanate-reactive compounds b1). In particular, these can be polyols. Polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane polyols can very particularly preferably be used as the isocyanate-reactive compound b1).

Als Polyesterpolyole sind beispielsweise lineare Polyesterdiole oder verzweigte Polyesterpolyole geeignet, die in bekannter Weise durch Umsetzung von aliphatischen, cycloaliphatischen oder aromatischen Di- bzw. Polycarbonsäuren bzw. ihren Anhydriden mit mehrwertigen Alkoholen einer OH-Funktionalität ≥ 2 erhalten werden können. Beispiele für geeignete Di- bzw. Polycarbonsäuren sind mehrwertige Carbonsäuren wie Bernstein-, Adipin-, Kork-, Sebacin-, Decandicarbon-, Phthal-, Terephthal-, Isophthal- Tetrahydrophthal- oder Trimellithsäure sowie Säureanhydride wie Phthal-, Trimellith- oder Bernsteinsäureanhydrid oder deren beliebige Gemische untereinander. Die Polyesterpolyole können auch auf natürlichen Rohstoffen wie Rizinusöl basieren. Es ist ebenfalls möglich, dass die Polyesterpolyole auf Homo- oder Mischpolymerisaten von Lactonen basieren, die bevorzugt durch Anlagerung von Lactonen bzw. Lactongemischen wie Butyrolacton, ε-Caprolacton und / oder Methyl-ε-caprolacton an hydroxyfunktionelle Verbindungen wie mehrwertige Alkohole einer OH-Funktionalität ≥ 2 beispielsweise der nachstehend genannten Art erhalten werden können.Suitable polyester polyols are, for example, linear polyester diols or branched polyester polyols which can be obtained in a known manner by reacting aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides with polyhydric alcohols having an OH functionality ≥ 2. Examples of suitable di- or polycarboxylic acids are polyvalent carboxylic acids such as succinic, adipic, cork, sebacic, decanedicarbonic, phthalic, terephthalic, isophthalic, tetrahydrophthalic or trimellitic acid and acid anhydrides such as phthalic, trimellitic or succinic anhydride or their arbitrary mixtures with each other. The polyester polyols can also be based on natural raw materials such as castor oil. It is also possible that the polyester polyols are based on homopolymers or copolymers of lactones, preferably by adding lactones or lactone mixtures such as butyrolactone, ε-caprolactone and / or methyl-ε-caprolactone to hydroxy-functional compounds such as polyhydric alcohols with an OH functionality ≥ 2 can be obtained for example of the type mentioned below.

Beispiele für geeignete Alkohole sind alle mehrwertigen Alkohole wie z.B. die C2 - C12-Diole, die isomeren Cyclohexandiole, Glycerin oder deren beliebige Gemische untereinander.Examples of suitable alcohols are all polyhydric alcohols, such as, for example, the C 2 -C 12 -diols, the isomeric cyclohexanediols, glycerol or any mixtures thereof with one another.

Geeignete Polycarbonatpolyole sind in an sich bekannter Weise durch Umsetzung von organischen Carbonaten oder Phosgen mit Diolen oder Diol-Mischungen zugänglich.Suitable polycarbonate polyols can be obtained in a manner known per se by reacting organic carbonates or phosgene with diols or diol mixtures.

Geeignete organische Carbonate sind Dimethyl-, Diethyl- und Diphenylcarbonat.Suitable organic carbonates are dimethyl, diethyl and diphenyl carbonate.

Geeignete Diole bzw. Mischungen umfassen die an sich im Rahmen der Polyestersegmente genannten mehrwertigen Alkohole einer OH-Funktionalität ≥ 2, bevorzugt Butandiol-1,4, Hexandiol-1,6 und / oder 3-Methylpentandiol. Auch Polyesterpolyole können zu Polycarbonatpolyolen umgearbeitet werden.Suitable diols or mixtures include the polyhydric alcohols mentioned per se in the context of the polyester segments with an OH functionality bevorzugt 2, preferably 1,4-butanediol, 1,6-hexanediol and / or 3-methylpentanediol. Polyester polyols can also be converted into polycarbonate polyols.

Geeignete Polyetherpolyole sind gegebenenfalls blockweise aufgebaute Polyadditionsprodukte cyclischer Ether an OH- oder NH-funktionelle Startermoleküle.Suitable polyether polyols are polyadducts of cyclic ethers with OH- or NH-functional starter molecules which are optionally built up in blocks.

Geeignete cyclische Ether sind beispielsweise Styroloxide, Ethylenoxid, Propylenoxid, Tetrahydrofuran, Butylenoxid, Epichlorhydrin sowie ihre beliebigen Mischungen.Suitable cyclic ethers are, for example, styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin and any mixtures thereof.

Als Starter können die an sich im Rahmen der Polyesterpolyole genannten mehrwertigen Alkohole einer OH-Funktionalität ≥ 2 sowie primäre oder sekundäre Amine und Aminoalkohole verwendet werden.The polyhydric alcohols having an OH functionality 2 2, which are mentioned per se in the context of the polyester polyols, and primary or secondary amines and amino alcohols can be used as starters.

Bevorzugte Polyetherpolyole sind solche der vorgenannten Art ausschließlich basierend auf Propylenoxid oder statistische oder Block-Copolymere basierend auf Propylenoxid mit weiteren 1-Alkylenoxiden. Besonders bevorzugt sind Propylenoxid-homopolymere sowie statistische oder Block-Copolymere, die Oxyethylen-, Oxypropylen- und / oder Oxybutyleneinheiten aufweisen, wobei der Anteil der Oxypropyleneinheiten bezogen auf die Gesamtmenge aller Oxyethylen-, Oxypropylen- und Oxybutyleneinheiten mindestens 20 Gew.-%, bevorzugt mindestens 45 Gew.-% ausmacht. Oxypropylen- und Oxybutylen umfasst hierbei alle jeweiligen linearen und verzweigten C3- und C4-Isomere.Preferred polyether polyols are those of the aforementioned type exclusively based on propylene oxide or random or block copolymers based on propylene oxide with further 1-alkylene oxides. Propylene oxide homopolymers and random or block copolymers which have oxyethylene, oxypropylene and / or oxybutylene units are particularly preferred, the proportion of oxypropylene units based on the total amount of all oxyethylene, oxypropylene and oxybutylene units being at least 20% by weight, preferably accounts for at least 45% by weight. Oxypropylene and oxybutylene include all linear and branched C 3 and C 4 isomers.

Daneben sind als Bestandteile der Polyol-Komponente b1) als polyfunktionelle, isocyanatreaktive Verbindungen auch niedermolekulare, d.h. mit Molekulargewichten ≤ 500 g/mol, kurzkettige, d.h. 2 bis 20 Kohlenstoffatome enthaltende aliphatische, araliphatische oder cycloaliphatische di-, tri- oder polyfunktionelle Alkohole geeignet.In addition, components of the polyol component b1) as polyfunctional, isocyanate-reactive compounds are also low molecular weight, i.e. with molecular weights ≤ 500 g / mol, short-chain, i.e. Aliphatic, araliphatic or cycloaliphatic di-, tri- or polyfunctional alcohols containing 2 to 20 carbon atoms are suitable.

Dies können beispielsweise in Ergänzung zu den oben genannten Verbindungen Neopentylglykol, 2-Ethyl-2-butylpropandiol, Trimethylpentandiol, stellungs-isomere Diethyloctandiole, Cyclohexandiol, 1,4-Cyclohexandimethanol, 1,6-Hexandiol, 1,2- und 1,4-Cyclohexandiol, hydriertes Bisphenol A, 2,2-Bis(4-hydroxy-cyclohexyl)-propan oder 2,2-Dimethyl-3-hydroxypropionsäure, 2,2-dimethyl-3-hydroxypropyl-ester sein. Beispiele geeigneter Triole sind Trimethylolethan, Trimethylolpropan oder Glycerin. Geeignete höherfunktionelle Alkohole sind Di-(trimethylolpropan), Pentaerythrit, Dipenta-erythrit oder Sorbit.This can, for example, in addition to the above-mentioned compounds neopentyl glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, positionally isomeric diethyloctanediols, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1,4- Cyclohexanediol, hydrogenated bisphenol A, 2,2-bis (4-hydroxy-cyclohexyl) propane or 2,2-dimethyl-3-hydroxypropionic acid, 2,2-dimethyl-3-hydroxypropyl ester. Examples of suitable triols are trimethylolethane, trimethylolpropane or glycerin. Suitable higher-functional alcohols are di- (trimethylolpropane), pentaerythritol, dipentaerythritol or sorbitol.

Besonders bevorzugt ist, wenn die Polyolkomponente ein difunktioneller Polyether-, Polyester oder ein Polyether-polyester-block-copolyester oder ein Polyether-Polyester-Blockcopolymer mit primären OH-Funktionen ist.It is particularly preferred if the polyol component is a difunctional polyether, polyester or a polyether-polyester block copolyester or a polyether-polyester block copolymer with primary OH functions.

Es ist ebenfalls möglich, als isocyanatreaktive Verbindungen b1) Amine einzusetzen. Beispiele geeigneter Amine sind Ethylendiamin, Propylendiamin, Diaminocyclohexan, 4,4'-Dicylohexylmethandiamin, Isophorondiamin (IPDA), difunktionelle Polyamine wie z.B. die Jeffamine®, aminterminierte Polymere, insbesondere mit zahlenmittleren Molmassen ≤ 10000 g/Mol. Mischungen der vorgenannten Amine können ebenfalls verwendet werden.It is also possible to use amines as the isocyanate-reactive compounds b1). Examples of suitable amines are ethylene diamine, propylene diamine, diaminocyclohexane, 4,4'-dicylohexyl methane diamine, isophorone diamine (IPDA), difunctional polyamines such as e.g. the Jeffamine®, amine-terminated polymers, in particular with number-average molar masses ≤ 10000 g / mol. Mixtures of the aforementioned amines can also be used.

Es ist ebenfalls möglich, als isocyanatreaktive Verbindungen b1) Aminoalkohole einzusetzen. Beispiele geeigneter Aminoalkohole sind die isomeren Aminoethanole, die isomere Aminopropanole die isomeren Aminobutanole und die isomeren Aminohexanole oder deren beliebige Mischungen.It is also possible to use amino alcohols as isocyanate-reactive compounds b1). Examples of suitable amino alcohols are the isomeric aminoethanols, the isomeric aminopropanols, the isomeric aminobutanols and the isomeric aminohexanols or any mixtures thereof.

Alle vorgenannten isocyanatreaktiven Verbindungen b1) können untereinander beliebig vermischt werden.All of the aforementioned isocyanate-reactive compounds b1) can be mixed with one another as desired.

Bevorzugt ist auch, wenn die isocyanatreaktiven Verbindungen b1) eine zahlenmittlere Molmasse von ≥ 200 und ≤ 10000 g/Mol, weiter bevorzugt ≥ 500 und ≤ 8000 g/Mol und ganz besonders bevorzugt ≥ 800 und ≤ 5000 g/Mol aufweisen. Die OH-Funktionalität der Polyole beträgt bevorzugt 1.5 bis 6.0, besonders bevorzugt 1.8 bis 4.0.It is also preferred if the isocyanate-reactive compounds b1) have a number-average molar mass of 200 200 and 100 10000 g / mol, more preferably 500 500 and 8 8000 g / mol and very particularly preferably 800 800 and 5000 5000 g / mol. The OH functionality of the polyols is preferably 1.5 to 6.0, particularly preferably 1.8 to 4.0.

Die Prepolymere der Polyisocyanat-Komponente a) können insbesondere einen Restgehalt an freiem monomeren Di- und Triisocyanaten < 1 Gew.-%, besonders bevorzugt < 0.5 Gew.-% und ganz besonders bevorzugt < 0.3 Gew.-% aufweisen.The prepolymers of polyisocyanate component a) can in particular have a residual free monomeric di- and triisocyanate content of <1% by weight, particularly preferably <0.5% by weight and very particularly preferably <0.3% by weight.

Es ist gegebenenfalls auch möglich, dass die Polyisocyanat-Komponente a) vollständig oder anteilsmäßig organische Verbindung enthält, deren NCO-Gruppen ganz oder teilweise mit aus der Beschichtungstechnologie bekannten Blockierungsmitteln umgesetzt sind. Beispiel für Blockierungsmittel sind Alkohole, Lactame, Oxime, Malonester, Pyrazole sowie Amine, wie z.B. Butanonoxim, Diisopropylamin, Malonsäurediethylester, Acetessigester, 3,5-Dimethylpyrazol, ε-Caprolactam, oder deren Mischungen.It is optionally also possible for the polyisocyanate component a) to contain all or part of the organic compound whose NCO groups have been reacted, in whole or in part, with blocking agents known from coating technology. Examples of blocking agents are alcohols, lactams, oximes, malonic esters, pyrazoles and amines, such as e.g. Butanone oxime, diisopropylamine, diethyl malonate, acetoacetic ester, 3,5-dimethylpyrazole, ε-caprolactam, or mixtures thereof.

Besonders bevorzugt ist, wenn die Polyisocyanat-Komponente a) Verbindungen mit aliphatisch gebundenen NCO-Gruppen umfasst, wobei unter aliphatisch gebundenen NCO-Gruppen derartige Gruppen verstanden werden, die an ein primäres C-Atom gebunden sind. Die isocyanatreaktive Komponente b) umfasst bevorzugt wenigstens eine organische Verbindung, die im Mittel wenigstens 1.5 und bevorzugt 2 bis 3 isocyanatreaktive Gruppen aufweist. Im Rahmen der vorliegenden Erfindung werden als isocyanatreaktive Gruppen bevorzugt Hydroxy-, Amino- oder MercaptoGruppen angesehen.It is particularly preferred if the polyisocyanate component a) comprises compounds with aliphatically bound NCO groups, aliphatically bound NCO groups being understood to mean those groups which are bound to a primary carbon atom. The isocyanate-reactive component b) preferably comprises at least one organic compound which has on average at least 1.5 and preferably 2 to 3 isocyanate-reactive groups. As part of the present Hydroxy, amino or mercapto groups are preferably regarded as isocyanate-reactive groups.

Die isocyanatreaktive Komponente kann insbesondere Verbindungen umfassen, die im Zahlenmittel wenigstens 1.5 und bevorzugt 2 bis 3 isocyanatreaktive Gruppen aufweisen.The isocyanate-reactive component can in particular comprise compounds which have a number average of at least 1.5 and preferably 2 to 3 isocyanate-reactive groups.

Geeignete polyfunktionelle, isocyanatreaktive Verbindungen der Komponente b) sind beispielsweise die oben beschriebenen Verbindungen b1).Suitable polyfunctional, isocyanate-reactive compounds of component b) are, for example, the compounds b1) described above.

Bei einer weiteren bevorzugten Ausführungsform ist vorgesehen, dass das Schreibmonomer c) wenigstens ein mono- und / oder ein multifunktionales Schreibmonomer umfasst oder daraus besteht. Weiter bevorzugt kann das Schreibmonomer wenigstens ein mono- und / oder ein multifunktionelles (Meth)acrylat-Schreibmonomer umfassen oder daraus bestehen. Ganz besonders bevorzugt kann das Schreibmonomer wenigstens ein mono- und / oder ein multifunktionelles Urethan-(meth)acrylat umfassen oder daraus bestehen.In a further preferred embodiment it is provided that the writing monomer c) comprises or consists of at least one mono- and / or a multifunctional writing monomer. More preferably, the writing monomer can comprise or consist of at least one mono- and / or a multifunctional (meth) acrylate writing monomer. The writing monomer can very particularly preferably comprise or consist of at least one mono- and / or a multifunctional urethane (meth) acrylate.

Geeignete Acrylat-Schreibmonomere sind insbesondere Verbindungen der allgemeinen Formel (II)

Figure imgb0002
bei denen n≥1 und n≤4 ist und R6 ein linearer, verzweigter, cyclischer oder heterocyclischer unsubstituierter oder gegebenenfalls auch mit Heteroatomen substituierter organischer Rest und/oder R7 Wasserstoff, ein linearer, verzweigter, cyclischer oder heterocyclischer unsubstituierter oder gegebenenfalls auch mit Heteroatomen substituierter organischer Rest ist. Besonders bevorzugt ist R7 Wasserstoff oder Methyl und/oder R6 ein linearer, verzweigter, cyclischer oder heterocyclischer unsubstituierter oder gegebenenfalls auch mit Heteroatomen substituierter organischer Rest.Suitable acrylate writing monomers are in particular compounds of the general formula (II)
Figure imgb0002
 in which n≥1 and n≤4 and R 6 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted with heteroatoms organic radical and / or R 7 is hydrogen, a linear, branched, cyclic or heterocyclic unsubstituted or optionally also Heteroatoms substituted organic radical. R 7 is particularly preferably hydrogen or methyl and / or R 6 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted with heteroatoms organic radical.

Als Acrylate bzw. Methacrylate werden vorliegend Ester der Acrylsäure bzw. Methacrylsäure bezeichnet. Beispiele bevorzugt verwendbarer Acrylate und Methacrylate sind Phenylacrylat, Phenylmethacrylat, Phenoxyethylacrylat, Phenoxyethylmethacrylat, Phenoxyethoxyethylacrylat, Phenoxyethoxyethylmethacrylat, Phenylthioethylacrylat, Phenylthioethylmethacrylat, 2-Naphthylacrylat, 2-Naphthylmethacrylat, 1,4-Bis-(2-thionaphthyl)-2-butylacrylat, 1,4-Bis-(2-thionaphthyl)-2-butylmethacrylat, Bisphenol A Diacrylat, Bisphenol A Dimethacrylat, sowie deren ethoxylierte Analogverbindungen, N-Carbazolylacrylate.In the present case, acrylates or methacrylates are esters of acrylic acid or methacrylic acid. Examples of acrylates and methacrylates which can be used with preference are phenyl acrylate, phenyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxyethoxyethyl acrylate, phenoxyethoxyethyl methacrylate, phenylthioethyl acrylate, phenylthioethyl methacrylate, 2-naphthylacrylate, 2-naphthyl-methyl-1,4-1,4-methacrylate, 1,4-butyl methacrylate - bis (2-thionaphthyl) -2-butyl methacrylate, Bisphenol A diacrylate, bisphenol A dimethacrylate, and their ethoxylated analog compounds, N-carbazolylacrylates.

Als Urethanacrylate werden vorliegend Verbindungen mit mindestens einer Acrylsäureestergruppe und mindestens eine Urethanbindung verstanden. Solche Verbindungen können beispielsweise durch Umsetzung eines Hydroxy-funktionellen Acrylats oder Methacrylats mit einer Isocyanatfunktionellen Verbindung erhalten werden.In the present case, urethane acrylates are understood to mean compounds with at least one acrylic ester group and at least one urethane bond. Such compounds can be obtained, for example, by reacting a hydroxy-functional acrylate or methacrylate with an isocyanate-functional compound.

Beispiele hierfür verwendbarer Isocyanat-funktionelle Verbindungen sind Monoisocyanate sowie die unter a) genannten monomeren Diisocyanate, Triisocyanate und / oder Polyisocyanate. Beispiele geeigneter Monoisocyanate sind Phenylisocyanat, die isomeren Methylthiophenylisocyanate. Di-, Tri- oder Polyisocyanate sind oben genannt sowie Triphenylmethan-4,4',4"-triisocyanat und Tris-(p-isocyanatophenyl)thiophosphat oder deren Derivate mit Urethan-, Harnstoff-, Carbodiimid-, Acylharnstoff-, Isocyanurat-, Allophanat-, Biuret-, Oxadiazintrion-, Uretdion-, Iminooxadiazindionstruktur und Mischungen derselben. Bevorzugt sind dabei aromatische Di-, Tri- oder Polyisocyanate.Examples of isocyanate-functional compounds which can be used for this purpose are monoisocyanates and the monomeric diisocyanates, triisocyanates and / or polyisocyanates mentioned under a). Examples of suitable monoisocyanates are phenyl isocyanate, the isomeric methylthiophenyl isocyanates. Di-, tri- or polyisocyanates are mentioned above, as well as triphenylmethane-4,4 ', 4 "-triisocyanate and tris (p-isocyanatophenyl) thiophosphate or their derivatives with urethane, urea, carbodiimide, acylurea, isocyanurate, Allophanate, biuret, oxadiazinetrione, uretdione, iminooxadiazinedione structure and mixtures thereof, preference being given to aromatic di-, tri- or polyisocyanates.

Als hydroxyfunktionelle Acrylate oder Methacrylate für die Herstellung von Urethanacrylaten kommen beispielsweise Verbindungen wie 2-Hydroxyethyl(meth)acrylat, Polyethylenoxid-mono-(meth)acrylate, Polypropylenoxidmono(meth)acrylate, Polyalkylenoxidmono(meth)-acrylate, Poly-(ε-caprolacton)mono(meth)acrylate, wie z.B. Tone® M100 (Dow, Schwalbach, DE), 2-Hydroxypropyl(meth)acrylat, 4-Hydroxybutyl(meth)acrylat, 3-Hydroxy-2,2-dimethylpropyl-(meth)acrylat, Hydroxypropyl(meth)acrylat, Acrylsäure-(2-hydroxy-3-phenoxypropylester), die hydroxyfunktionellen Mono-, Di- oder Tetraacrylate mehrwertiger Alkohole wie Trimethylolpropan, Glycerin, Pentaerythrit, Dipentaerythrit, ethoxyliertes, propoxyliertes oder alkoxyliertes Trimethylolpropan, Glycerin, Pentaerythrit, Dipentaerythrit oder deren technische Gemische. Bevorzugt sind 2-Hydroxyethylacrylat, Hydroxypropylacrylat, 4-Hydroxybutylacrylat und Poly(ε-caprolacton)mono-(meth)acrylat.Hydroxy-functional acrylates or methacrylates for the production of urethane acrylates include, for example, compounds such as 2-hydroxyethyl (meth) acrylate, polyethylene oxide mono- (meth) acrylates, polypropylene oxide mono (meth) acrylates, polyalkylene oxide mono (meth) acrylates, poly (ε-caprolactone) ) mono (meth) acrylates, such as Tone® M100 (Dow, Schwalbach, DE), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, hydroxypropyl (meth) acrylate, acrylic acid (2-hydroxy-3-phenoxypropyl ester), the hydroxy-functional mono-, di- or tetraacrylates of polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or their technical mixture. 2-Hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate and poly (ε-caprolactone) mono- (meth) acrylate are preferred.

Ebenfalls verwendet werden können die an sich bekannten hydroxylgruppenhaltigen Epoxy(meth)-acrylate mit OH-Gehalten von 20 bis 300 mg KOH/g oder hydroxylgruppenhaltige Polyurethan-(meth)acrylate mit OH-Gehalten von 20 bis 300 mg KOH/g oder acrylierte Polyacrylate mit OH-Gehalten von 20 bis 300 mg KOH/g sowie deren Mischungen untereinander und Mischungen mit hydroxylgruppenhaltigen ungesättigten Polyestern sowie Mischungen mit Polyester(meth)acrylaten oder Mischungen hydroxylgruppenhaltiger ungesättigter Polyester mit Polyester(meth)acrylaten.Also known are the hydroxyl-containing epoxy (meth) acrylates with OH contents of 20 to 300 mg KOH / g or hydroxyl-containing polyurethane (meth) acrylates with OH contents of 20 to 300 mg KOH / g or acrylated polyacrylates with OH contents of 20 to 300 mg KOH / g and their mixtures with one another and mixtures with hydroxyl-containing unsaturated polyesters and mixtures with polyester (meth) acrylates or mixtures of hydroxyl-containing unsaturated polyesters with polyester (meth) acrylates.

Bevorzugt sind insbesondere Urethanacrylate erhältlich aus der Umsetzung von Tris(p-isocyanatophenyl)thiophosphat und / oder m-Methylthiophenylisocyanat mit alkoholfunktionellen Acrylaten wie Hydroxyethyl(meth)acrylat, Hydroxypropyl(meth)acrylat und / oder Hydroxybutyl(meth)-acrylat.Urethane acrylates obtained from the reaction of tris (p-isocyanatophenyl) thiophosphate and / or m-methylthiophenyl isocyanate with alcohol-functional acrylates are particularly preferred such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and / or hydroxybutyl (meth) acrylate.

Ebenso ist es möglich, dass das Schreibmonomer weitere ungesättigte Verbindungen wie α,β-ungesättigte Carbonsäurederivate wie beispielsweise Maleinate, Fumarate, Maleimide, Acrylamide, weiterhin Vinylether, Propenylether, Allylether und Dicyclopentadienyl-Einheiten enthaltende Verbindungen sowie olefinisch ungesättigte Verbindungen wie z.B. Styrol, α-Methylstyrol, Vinyltoluol und / oder Olefine, umfasst oder daraus besteht.It is also possible for the writing monomer to contain further unsaturated compounds such as α, β-unsaturated carboxylic acid derivatives such as maleinates, fumarates, maleimides, acrylamides, compounds containing vinyl ethers, propenyl ethers, allyl ethers and dicyclopentadienyl units as well as olefinically unsaturated compounds such as e.g. Styrene, α-methylstyrene, vinyltoluene and / or olefins, comprises or consists thereof.

Photoinitiatoren der Komponente d) sind üblicherweise durch aktinische Strahlung aktivierbare Verbindungen, die eine Polymerisation der Schreibmonomere auslösen können. Bei den Photoinitiatoren kann zwischen unimolekularen (Typ I) und bimolekularen (Typ II) Initiatoren unterschieden werden. Des Weiteren werden sie je nach ihrer chemischen Natur in Photoinitiatoren für radikalische, anionische, kationische oder gemischte Art der Polymerisation unterschieden.Photoinitiators of component d) are usually compounds which can be activated by actinic radiation and can trigger polymerization of the writing monomers. In the case of photoinitiators, a distinction can be made between unimolecular (type I) and bimolecular (type II) initiators. Furthermore, depending on their chemical nature, they are differentiated into photoinitiators for radical, anionic, cationic or mixed types of polymerization.

Typ I-Photoinitiatoren (Norrish-Typ-I) für die radikalische Photopolymerisation bilden beim Bestrahlen durch eine unimolekulare Bindungsspaltung freie Radikale. Beispiele für Typ I-Photoinitiatoren sind Triazine, Oxime, Benzoinether, Benzilketale, Bis-imidazole, Aroylphosphinoxide, Sulfonium- und Iodoniumsalze.Type I photoinitiators (Norrish type I) for radical photopolymerization form free radicals when irradiated by unimolecular bond cleavage. Examples of type I photoinitiators are triazines, oximes, benzoin ethers, benzil ketals, bis-imidazoles, aroylphosphine oxides, sulfonium and iodonium salts.

Typ II-Photoinitiatoren (Norrish-Typ-II) für die radikalische Polymerisation bestehen aus einem Farbstoff als Sensibilisator und einem Coinitiator und durchlaufen bei der Bestrahlung mit auf den Farbstoff angepasstem Licht eine bimolekulare Reaktion. Zunächst absorbiert der Farbstoff ein Photon und überträgt aus einem angeregten Zustand Energie auf den Coinitiator. Dieser setzt durch Elektronen- oder Protonentransfer oder direkte Wasserstoffabstraktion die polymerisationsauslösenden Radikale frei.Type II photoinitiators (Norrish type II) for radical polymerization consist of a dye as a sensitizer and a coinitiator and undergo a bimolecular reaction when irradiated with light adapted to the dye. First, the dye absorbs a photon and transfers energy to the coinitiator from an excited state. This releases the radicals that trigger polymerization by electron or proton transfer or direct hydrogen abstraction.

Im Sinne dieser Erfindung werden bevorzugt Typ II-Photoinitiatoren verwendet.For the purposes of this invention, type II photoinitiators are preferably used.

Solche Photoinitiatorsysteme sind prinzipiell in der EP 0 223 587 A beschriebenen und bestehen bevorzugt aus einer Mischung von einem oder mehreren Farbstoffen mit Ammoniumalkylarylborat(en).Such photoinitiator systems are in principle in the EP 0 223 587 A described and preferably consist of a mixture of one or more dyes with ammonium alkylaryl borate (s).

Geeignete Farbstoffe, die zusammen mit einem Ammoniumalkylarylborat einen Typ II-Photoinitiator bilden, sind die in der WO 2012062655 beschriebenen kationischen Farbstoffe in Kombination mit den eben dort beschriebenen Anionen.Suitable dyes which form a type II photoinitiator together with an ammonium alkylaryl borate are those in US Pat WO 2012062655 described cationic dyes in combination with the anions just described there.

Unter kationischen Farbstoffen werden bevorzugt solche der folgenden Klassen verstanden: Acridin-Farbstoffe, Xanthen-Farbstoffe, Thioxanthen-Farbstoffe, Phenazin-Farbstoffe, Phenoxazin-Farbstoffe, Phenothiazin-Farbstoffe, Tri(het)arylmethan-Farbstoffe - insbesondere Diamino- und Triamino(het)arylmethan-Farbstoffe, Mono-, Di-, Tri- und Pentamethincyanin-Farbstoffe, Hemicyanin-Farbstoffe, extern kationische Merocyanin-Farbstoffe, extern kationische Neutrocyanin-Farbstoffe, Nullmethin-Farbstoffe - insbesondere Naphtholactam-Farbstoffe, Streptocyanin-Farbstoffe. Solche Farbstoffe sind beispielsweise in H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Azine Dyes, Wiley-VCH Verlag, 2008 , H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Methine Dyes and Pigments, Wiley-VCH Verlag, 2008 , T. Gessner, U. Mayer in Ullmann's Encyclopedia of Industrial Chemistry, Triarylmethane and Diarylmethane Dyes, Wiley-VCH Verlag, 2000 beschrieben.Cationic dyes are preferably understood to mean those of the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes, phenoxazine dyes, Phenothiazine dyes, tri (het) arylmethane dyes - in particular diamino and triamino (het) arylmethane dyes, mono-, di-, tri- and pentamethinecyanine dyes, hemicyanine dyes, externally cationic merocyanine dyes, externally cationic neutrocyanine Dyes, zero methine dyes - especially naphtholactam dyes, streptocyanin dyes. Such dyes are for example in H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Azine Dyes, Wiley-VCH Verlag, 2008 , H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Methine Dyes and Pigments, Wiley-VCH Verlag, 2008 , T. Gessner, U. Mayer in Ullmann's Encyclopedia of Industrial Chemistry, Triarylmethane and Diarylmethane Dyes, Wiley-VCH Verlag, 2000 described.

Besonders bevorzugt sind Phenazin-Farbstoffe, Phenoxazin-Farbstoffe, Phenothiazin-Farbstoffe, Tri(het)arylmethan-Farbstoffe - insbesondere Diamino- und Triamino(het)arylmethan-Farbstoffe, Mono-, Di-, Tri- und Pentamethincyanin-Farbstoffe, Hemicyanin-Farbstoffe, Nullmethin-Farbstoffe - insbesondere Naphtholactam-Farbstoffe, Streptocyanin-Farbstoffe.Phenazine dyes, phenoxazine dyes, phenothiazine dyes, tri (het) arylmethane dyes - in particular diamino and triamino (het) arylmethane dyes, mono-, di-, tri- and pentamethinecyanine dyes, hemicyanine dyes, are particularly preferred. Dyes, zero methine dyes - especially naphtholactam dyes, streptocyanine dyes.

Beispiele für kationische Farbstoffe sind Astrazon Orange G, Basic Blue 3, Basic Orange 22, Basic Red 13, Basic Violett 7, Methylenblau, Neu Methylenblau, Azur A, 2,4-Diphenyl-6-(4-methoxyphenyl)pyrylium, Safranin O, Astraphloxin, Brilliant Grün, Kristallviolett, Ethylviolett und Thionin.Examples of cationic dyes are Astrazon Orange G, Basic Blue 3, Basic Orange 22, Basic Red 13, Basic Violet 7, Methylene Blue, New Methylene Blue, Azure A, 2,4-Diphenyl-6- (4-methoxyphenyl) pyrylium, Safranin O , Astraphloxin, brilliant green, crystal violet, ethyl violet and thionine.

Bevorzugte Anionen sind insbesondere C8- bis C25-Alkansulfonat, vorzugsweise C13- bis C25-Alkansulfonat, C3- bis C18-Perfluoralkansulfonat, C4- bis C18-Perfluoralkansulfonat, das in der Alkylkette mindestens 3 Wasserstoffatome trägt, C9- bis C25-Alkanoat, C9- bis C25-Alkenoat, C8- bis C25-Alkylsulfat, vorzugsweise C13- bis C25-Alkylsulfat, C8- bis C25-Alkenylsulfat, vorzugsweise C13- bis C25-Alkenylsulfat, C3- bis C18-Perfluoralkylsulfat, C4- bis C18-Perfluoralkylsulfat, das in der Alkylkette mindestens 3 Wasserstoffatome trägt, Polyethersulfate basierend auf mindestens 4 Äquivalenten Ethylenoxid und/oder 4 Äquivalenten Propylenoxid, Bis-C4- bis C25-Alkyl-, C5- bis C7-Cycloalkyl-, C3- bis C8-Alkenyl- oder C7- bis C11-Aralkyl-sulfosuccinat, durch mindestens 8 Fluoratome substituiertes Bis-C2- bis C10-alkyl-sulfosuccinat, C8- bis C25-Alkyl-sulfoacetate, durch mindestens einen Rest der Gruppe Halogen, C4- bis C25-Alkyl, Perfluor-C1- bis C8-Alkyl und/oder C1- bis C12-Alkoxycarbonyl substituiertes Benzolsulfonat, ggf. durch Nitro, Cyano, Hydroxy, C1- bis C25-Alkyl, C1- bis C12-Alkoxy, Amino, C1- bis C12-Alkoxycarbonyl oder Chlor substituiertes Naphthalin- oder Biphenylsulfonat, ggf. durch Nitro, Cyano, Hydroxy, C1- bis C25-Alkyl, C1- bis C12-Alkoxy, C1- bis C12-Alkoxycarbonyl oder Chlor substituiertes Benzol-, Naphthalin- oder Biphenyldisulfonat, durch Dinitro, C6- bis C25-Alkyl, C4- bis C12-Alkoxycarbonyl, Benzoyl, Chlorbenzoyl oder Toluoyl substituiertes Benzoat, das Anion der Naphthalindicarbonsäure, Diphenyletherdisulfonat, sulfonierte oder sulfatierte, ggf. mindestens einfach ungesättigte C8- bis C25-Fettsäureester von aliphatischen C1- bis C8-Alkoholen oder Glycerin, Bis-(sulfo-C2- bis C6-alkyl)-C3- bis C12-alkandicarbonsäureester, Bis-(sulfo-C2- bis C6-alkyl)-itaconsäureester, (Sulfo-C2- bis C6-alkyl)-C6- bis C18-alkancarbonsäureester, (Sulfo-C2- bis C6-alkyl)-acryl- oder methacrylsäureester, ggf. durch bis zu 12 Halogenreste substituiertes Triscatecholphosphat, ein Anion der Gruppe Tetraphenylborat, Cyanotriphenylborat, Tetraphenoxyborat, C4- bis C12-Alkyl-triphenylborat, deren Phenyl- oder Phenoxy-Reste durch Halogen, C1- bis C4-Alkyl und/oder C1- bis C4-Alkoxy substituiert sein können, C4- bis C12-Alkyl-trinaphthylborat, Tetra-Ci- bis C20-alkoxyborat, 7,8- oder 7,9-Dicarba-nido-undecaborat(1-) oder (2-), die gegebenenfalls an den B- und/oder C-Atomen durch eine oder zwei C1- bis C12-Alkyl- oder Phenyl-Gruppen substituiert sind, Dodecahydrodicarbadodecaborat(2-) oder B-C1- bis C12-Alkyl-C-phenyl-dodecahydro-dicarbadodecaborat(1-) steht, wobei bei mehrwertigen Anionen wie Naphthalindisulfonat A- für ein Äquivalent dieses Anions steht, und wobei die Alkan- und Alkylgruppen verzweigt sein können und/oder durch Halogen, Cyano, Methoxy, Ethoxy, Methoxycarbonyl oder Ethoxycarbonyl substituiert sein können.Preferred anions are in particular C 8 to C 25 alkanesulfonate, preferably C 13 to C 25 alkanesulfonate, C 3 to C 18 perfluoroalkanesulfonate, C 4 to C 18 perfluoroalkanesulfonate which carries at least 3 hydrogen atoms in the alkyl chain, C 9 to C 25 alkanoate, C 9 to C 25 alkenoate, C 8 to C 25 alkyl sulfate, preferably C 13 to C 25 alkyl sulfate, C 8 to C 25 alkenyl sulfate, preferably C 13 to C 25 alkenyl sulfate, C 3 to C 18 perfluoroalkyl sulfate, C 4 to C 18 perfluoroalkyl sulfate which carries at least 3 hydrogen atoms in the alkyl chain, polyether sulfates based on at least 4 equivalents of ethylene oxide and / or 4 equivalents of propylene oxide, bis-C 4 - to C 25 -alkyl, C 5 - to C 7 -Cycloa l alkyl-, C 3 - to C 8 -alkenyl or C 7 - to C aralkyl sulfosuccinate 11, by at least 8 fluorine atoms substituted bis-C 2 to C 10 alkyl sulfosuccinate, C 8 to C 25 alkyl sulfoacetates, by at least one radical from the group halogen, C 4 to C 25 -Alkyl, perfluoro-C 1 - to C 8 -alkyl and / or C 1 - to C 12 -alkoxycarbonyl substituted benzenesulfonate, optionally substituted by nitro, cyano, hydroxy, C 1 - to C 25 -alkyl, C 1 - to C 12 -alkoxy, amino, C 1 - to C 12 -alkoxycarbonyl or chlorine-substituted naphthalene or biphenyl sulfonate, optionally with nitro, cyano, hydroxy, C 1 - to C 25 -alkyl, C 1 - to C 12 -alkoxy, C 1 - to C 12 -alkoxycarbonyl or chlorine-substituted benzene, naphthalene or biphenyl disulfonate, dinitro, C 6 - to C 25 -alkyl, C 4 - to C 12 -alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl-substituted benzoate, the anion of Naphthalenedicarboxylic acid, diphenyl ether disulfonate, sulfonated or sulfated, optionally at least monounsaturated C 8 to C 25 fatty acid esters from aliphatic C 1 to C 8 alcohols or glycerol, bis (sulfo-C 2 to C 6 alkyl) C 3 to C 12 alkanedicarboxylic acid esters, bis (sulfo C 2 to C 6 alkyl) ) -itaconic acid esters, (sulfo-C 2 - to C 6 -alkyl) -C 6 - to C 18 -alkanecarboxylic acid esters, (sulfo-C 2 - to C 6 -alkyl) -acrylic or methacrylic acid esters, optionally by up to 12 Halogen-substituted triscatechol phosphate, an anion of the group tetraphenylborate, cyanotriphenylborate, tetraphenoxyborate, C 4 - to C 12 -alkyl triphenylborate, the phenyl or phenoxy radicals thereof by halogen, C 1 - to C 4 -alkyl and / or C 1 - bis C 4 -alkoxy may be substituted, C 4 - to C 12 -alkyltrinaphthylborate, tetra-Ci- to C 20 -alkoxyborate, 7,8- or 7,9-dicarba-nido-undecaborate (1-) or (2 -), which are optionally substituted on the B and / or C atoms by one or two C 1 - to C 12 -alkyl or phenyl groups, dodecahydrodicarbadodecaborate (2-) or BC 1 - to C 12 -alkyl- C-phenyl-dodecahydro-dicarbadodecaborate (1-) stands, wob ei in the case of polyvalent anions such as naphthalene disulfonate A - represents one equivalent of this anion, and the alkane and alkyl groups can be branched and / or can be substituted by halogen, cyano, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl.

Bevorzugt ist auch, wenn das Anion A- des Farbstoffs einen AClogP im Bereich von 1 bis 30, besonders bevorzugt im Bereich von 1 bis 12 und insbesondere bevorzugt im Bereich von 1 bis 6,5 aufweist. Der AClogP wird nach J. Comput. Aid. Mol. Des. 2005, 19, 453; Virtual Computational Chemistry Laboratory, http://www.vcclab.org berechnet .It is also preferred if the anion A - of the dye has an AClogP in the range from 1 to 30, particularly preferably in the range from 1 to 12 and particularly preferably in the range from 1 to 6.5. The AClogP is after J. Comput. Aid. Mol. Des. 2005, 19, 453; Virtual Computational Chemistry Laboratory, http://www.vcclab.org .

Geeignete Ammoniumalkylarylborate sind beispielsweise ( Cunningham et al., RadTech'98 North America UV/EB Conference Proceedings, Chicago, Apr. 19-22, 1998 ): Tetrabutylammonium Triphenylhexylborat, Tetrabutylammonium Triphenylbutylborat, Tetrabutylammonium Trinapthylhexylborat, Tetrabutylammonium Tris(4-tert.butyl)-phenylbutylborat, Tetrabutylammonium Tris-(3-fluorphenyl)-hexylborat hexylborat ([191726-69-9], CGI 7460, Produkt der BASF SE, Basel, Schweiz), 1-Methyl-3-octylimidazolium Dipentyldiphenylborat und Tetrabutylammonium Tris-(3-chlor-4-methylphenyl)-hexylborat ([1147315-11-4], CGI 909, Produkt der BASF SE, Basel, Schweiz).Suitable ammonium alkylaryl borates are, for example ( Cunningham et al., RadTech'98 North America UV / EB Conference Proceedings, Chicago, Apr. 19-22, 1998 ): Tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinapthylhexylborate, tetrabutylammonium tris (4-tert.butyl) phenylbutylborate, BASF tetrabutylammonium tris (3-fluorophenyl) 19, hexa- (60-hexylate), (26-hexylborate), tris (3-fluorophenyl) 19-, (26-fluorophenyl), tris (3-fluorophenyl) 19-, , Basel, Switzerland), 1-methyl-3-octylimidazolium dipentyldiphenylborate and tetrabutylammonium tris (3-chloro-4-methylphenyl) hexylborate ([1147315-11-4], CGI 909, product of BASF SE, Basel, Switzerland) .

Es kann vorteilhaft sein, Gemische dieser Photoinitiatoren einzusetzen. Je nach verwendeter Strahlungsquelle muss Typ und Konzentration an Photoinitiator in dem Fachmann bekannter Weise angepasst werden. Näheres ist zum Beispiel in P. K. T. Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3, 1991, SITA Technology, London, S. 61 - 328 beschrieben.It can be advantageous to use mixtures of these photoinitiators. Depending on the radiation source used, the type and concentration of photoinitiator must be adapted in a manner known to the person skilled in the art. More information is, for example, in PKT Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3, 1991, SITA Technology, London, pp. 61 - 328 described.

Ganz besonders bevorzugt ist, wenn der Photoinitiator eine Kombination von Farbstoffen, deren Absorptionsspektren zumindest teilweise den Spektralbereich von 400 bis 800 nm abdecken, mit wenigstens einem auf die Farbstoffe abgestimmten Coinitiator umfasst.It is very particularly preferred if the photoinitiator comprises a combination of dyes, the absorption spectra of which at least partially cover the spectral range from 400 to 800 nm, with at least one coinitiator matched to the dyes.

Bevorzugt ist auch, wenn wenigstens ein für eine Laserlichtfarbe ausgewählt aus blau, grün und rot geeigneter Photoinitiator in der Photopolymer-Formulierung enthalten ist.It is also preferred if at least one photoinitiator suitable for a laser light color selected from blue, green and red is contained in the photopolymer formulation.

Weiter bevorzugt ist auch, wenn die Photopolymer-Formulierung für wenigstens zwei Laserlichtfarben ausgewählt aus blau, grün und rot je einen geeigneten Photoinitiator enthält.It is also preferred if the photopolymer formulation contains a suitable photoinitiator for at least two laser light colors selected from blue, green and red.

Ganz besonders bevorzugt ist schließlich, wenn die Photopolymer-Formulierung für jede der Laserlichtfarben blau, grün und rot jeweils einen geeigneten Photoinitiator enthält.Finally, it is very particularly preferred if the photopolymer formulation contains a suitable photoinitiator for each of the laser light colors blue, green and red.

Gemäß einer weiteren bevorzugten Ausführungsform ist vorgesehen, dass die Photopolymer-Formulierung zusätzlich Urethane als Additive enthält, wobei die Urethane insbesondere mit wenigstens einem Fluoratom substituiert sein können.According to a further preferred embodiment it is provided that the photopolymer formulation additionally contains urethanes as additives, it being possible for the urethanes to be substituted in particular with at least one fluorine atom.

Bevorzugt können die Urethane die allgemeine Formel (III)

Figure imgb0003
haben, in der m≥1 und m≤8 ist und R8, R9 und R10 lineare, verzweigte, cyclische oder heterocyclische unsubstituierte oder gegebenenfalls auch mit Heteroatomen substituierte organische Reste und/oder R9, R10 unabhängig voneinander Wasserstoff sind, wobei bevorzugt mindestens einer der Reste R8, R9, R10 mit wenigstens einem Fluoratom substituiert ist und besonders bevorzugt R8 ein organischer Rest mit mindestens einem Fluoratom ist. Besonders bevorzugt ist R9 ein linearer, verzweigter, cyclischer oder heterocyclischer unsubstituierter oder gegebenenfalls auch mit Heteroatomen wie beispielsweise Fluor substituierter organischer Rest.The urethanes can preferably have the general formula (III)
Figure imgb0003
 in which m≥1 and m≤8 and R 8 , R 9 and R 10 are linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted with heteroatoms, organic radicals and / or R 9 , R 10 are independently hydrogen, wherein preferably at least one of the radicals R 8 , R 9 , R 10 is substituted with at least one fluorine atom and particularly preferably R 8 is an organic radical with at least one fluorine atom. R 9 is particularly preferably a linear, branched, cyclic or heterocyclic unsubstituted or optionally also organic radical substituted with heteroatoms such as fluorine.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Photopolymer umfassend Matrixpolymere, ein Schreibmonomer und einen Photoinitiator, das zusätzlich eine Verbindung der Formel (I) umfasst

Figure imgb0004
worin

A1, A2, A3
jeweils unabhängig voneinander Wasserstoff, Fluor, Chlor, Brom oder Iod,
R1, R2, R3, R4, R5
jeweils unabhängig voneinander Wasserstoff, Halogen, Cyano, Nitro, Amino, Alkylimino, Azid, Isonitril, Enamino, Formyl, Acyl, Carboxyl, Carbonester, Carbonamid, Orthoester, Sulfonat, Phosphat, Organosulfonyl, Organo-sulfoxidyl, gegebenenfalls fluoriertes Alkoxy oder ein gegebenenfalls substituierter aromatischer, heteroaromatischer, aliphatischer, araliphatischer, olefinischer oder acetylenischer Rest sind und geeignete Reste über eine Brücke beliebiger Substitution miteinander verbunden sein können oder dass zwei oder mehrere Verbindungen der Formel (I) über mindestens einen der Reste R1, R2, R3, R4, R5 verbunden sein können, wobei diese Reste dann eine 2 - 4-fach funktionelle Brücke darstellen können, mit der Maßgabe, dass wenigstens einer der Reste R1, R2, R3, R4, R5 nicht Wasserstoff ist. Gemäß einer bevorzugten Ausführungsform des erfindungsgemäßen Photopolymers ist vorgesehen, dass bei der Verbindung der Formel (I) A1, A2 und A3 jeweils unabhängig voneinander Fluor, Chlor, Brom oder Iod und weiter bevorzugt A1, A2 und A3 gleichzeitig entweder Fluor, Chlor, Brom oder Iod sind. Ebenfalls bevorzugt ist, wenn bei der Verbindung der Formel (I) R1, R2, R3, R4, R5 jeweils unabhängig voneinander Wasserstoff, Halogen, Cyano, Nitro, Isonitril, Acyl, Carboxyl, Carbonester, Carbonamid, Orthoester, Sulfonat, Phosphat, Organo-sulfonyl, Organo-sulfoxidyl, gegebenenfalls fluoriertes Alkoxy und bevorzugt Wasserstoff, Halogen, Cyano, Nitro, Isonitril, Acyl, Carboxyl, weiter bevorzugt Wasserstoff, Halogen und besonders bevorzugt Wasserstoff, Fluor, Chlor, Brom oder Iod sind.
The present invention further provides a photopolymer comprising matrix polymers, a writing monomer and a photoinitiator which additionally comprises a compound of the formula (I)
Figure imgb0004
 wherein
A 1 , A 2 , A 3
each independently of one another hydrogen, fluorine, chlorine, bromine or iodine,
R 1 , R 2 , R 3 , R 4 , R 5
each independently of one another hydrogen, halogen, cyano, nitro, amino, alkylimino, azide, isonitrile, enamino, formyl, acyl, carboxyl, carbonate ester, carbonamide, orthoester, sulfonate, phosphate, organosulfonyl, organosulfoxidyl, optionally fluorinated alkoxy or an optionally substituted one aromatic, heteroaromatic, aliphatic, araliphatic, olefinic or acetylenic radical and suitable radicals can be connected to one another via a bridge of any substitution or that two or more compounds of the formula (I) have at least one of the radicals R 1 , R 2 , R 3 , R 4 , R 5 can be connected, these radicals then being able to represent a 2-4-fold functional bridge, with the proviso that at least one of the radicals R 1 , R 2 , R 3 , R 4 , R 5 is not hydrogen . According to a preferred embodiment of the photopolymer according to the invention, it is provided that in the compound of the formula (I) A 1 , A 2 and A 3 are each independently fluorine, chlorine, bromine or iodine and more preferably A 1 , A 2 and A 3 either simultaneously Are fluorine, chlorine, bromine or iodine. It is also preferred if, in the case of the compound of the formula (I) R 1 , R 2 , R 3 , R 4 , R 5, in each case independently of one another, hydrogen, halogen, cyano, nitro, isonitrile, acyl, carboxyl, carbonate ester, carbonamide, orthoester, Sulfonate, phosphate, organosulfonyl, organosulfoxidyl, optionally fluorinated alkoxy and preferably hydrogen, halogen, cyano, nitro, isonitrile, acyl, carboxyl, more preferably hydrogen, halogen and particularly preferably hydrogen, fluorine, chlorine, bromine or iodine.

Die Matrixpolymere des erfindungsgemäßen Photopolymers können insbesondere vernetzt und besonders bevorzugt dreidimensional vernetzt sein.The matrix polymers of the photopolymer according to the invention can in particular be cross-linked and particularly preferably three-dimensionally cross-linked.

Vorteilhaft ist auch, wenn die Matrixpolymere Polyurethane sind, wobei die die Polyurethane insbesondere durch Umsetzung wenigstens einer Polyisocyanat-Komponente mit wenigstens einer Isocyanat-reaktiven Komponente erhältlich sein können.It is also advantageous if the matrix polymers are polyurethanes, the polyurethanes being obtainable in particular by reacting at least one polyisocyanate component with at least one isocyanate-reactive component.

Die oben zu der erfindungsgemäßen Photopolymer-Formulierung getroffenen Aussagen bezüglich weiterer bevorzugten Ausführungsformen gelten analog auch für das erfindungsgemäße Photopolymer.The statements made above regarding the photopolymer formulation according to the invention with regard to further preferred embodiments also apply analogously to the photopolymer according to the invention.

Gegenstand der Erfindung ist auch ein holographisches Medium insbesondere in Form eines Films, enthaltend ein erfindungsgemäßes Photopolymer oder erhältlich unter Verwendung einer erfindungsgemäßen Photopolymer-Formulierung. Noch ein weiterer Gegenstand der Erfindung ist die Verwendung einer erfindungsgemäßen Photopolymer-Formulierung zur Herstellung holographischer Medien.The invention also relates to a holographic medium, in particular in the form of a film, containing a photopolymer according to the invention or obtainable using a photopolymer formulation according to the invention. Another object of the invention is the use of a photopolymer formulation according to the invention for the production of holographic media.

Bei einer bevorzugten Ausführungsform des erfindungsgemäßen holographisches Mediums sind in dieses holgraphische Informationen einbelichtet.In a preferred embodiment of the holographic medium according to the invention, holographic information is imprinted therein.

Die erfindungsgemäßen holographischen Medien können durch entsprechende Belichtungsprozesse für optische Anwendungen im gesamten sichtbaren und nahen UV-Bereich (300-800 nm) zu Hologrammen verarbeitet werden können. Visuelle Hologramme umfassen alle Hologramme, die nach dem Fachmann bekannten Verfahren aufgezeichnet werden können. Darunter fallen unter anderem In-Line (Gabor) Hologramme, Off-Axis Hologramme, Full-Aperture Transfer Hologramme, Weißlicht-Transmissionshologramme ("Regenbogenhologramme), Denisyukhologramme, Off-Axis Reflektionshologramme, Edge-Lit Hologramme sowie holographische Stereogramme. Bevorzugt sind Reflektionshologramme, Denisyukhologramme, Transmissionshologramme.The holographic media according to the invention can be processed into holograms by appropriate exposure processes for optical applications in the entire visible and near UV range (300-800 nm). Visual holograms include all holograms that can be recorded by methods known to those skilled in the art. These include in-line (Gabor) holograms, off-axis holograms, full-aperture transfer holograms, white-light transmission holograms ("rainbow holograms), Denisyukholograms, off-axis reflection holograms, edge-lit holograms and holographic stereograms. Denisyukholograms, transmission holograms.

Mögliche optische Funktionen der Hologramme, die mit den erfindungsgemäßen Photopolymer-Formulierungen hergestellt werden können entsprechen den optische Funktionen von Lichtelementen wie Linsen, Spiegel, Umlenkspiegel, Filter, Streuscheiben, Beugungselemente, Diffusoren, Lichtleiter, Lichtlenker (waveguides), Projektionsscheiben und/oder Masken. Ebenfalls können Kombinationen aus dies optischen Funktionen unabhängig voneinander in einem Hologramm vereinigt sein. Häufig zeigen diese optischen Elemente eine Frequenzselektivität, je nachdem wie die Hologramme belichtet wurden und welche Dimensionen das Hologramm hat.Possible optical functions of the holograms that can be produced with the photopolymer formulations according to the invention correspond to the optical functions of light elements such as lenses, mirrors, deflecting mirrors, filters, diffusing screens, diffraction elements, diffusers, light guides, light guides (waveguides), projection screens and / or masks. Combinations of these optical functions can also be combined independently of one another in a hologram. These optical elements often show frequency selectivity, depending on how the holograms were exposed and what dimensions the hologram has.

Zudem können mittels der erfindungsgemäßen Medien auch holographische Bilder oder Darstellungen hergestellt werden, wie zum Beispiel für persönliche Portraits, biometrische Darstellungen in Sicherheitsdokumenten, oder allgemein von Bilder oder Bildstrukturen für Werbung, Sicherheitslabels, Markenschutz, Markenbranding, Etiketten, Designelementen, Dekorationen, Illustrationen, Sammelkarten, Bilder und dergleichen sowie Bilder, die digitale Daten repräsentieren können u.a. auch in Kombination mit den zuvor dargestellten Produkten. Holographische Bilder können den Eindruck eines dreidimensionalen Bildes haben, sie können aber auch Bildsequenzen, kurze Filme oder eine Anzahl von verschiedenen Objekten darstellen, je nachdem aus welchem Winkel, mit welcher (auch bewegten) Lichtquelle etc. diese beleuchtet wird. Aufgrund dieser vielfältigen Design-Möglichkeiten stellen Hologramme, insbesondere Volumenhologramme, eine attraktive technische Lösung für die oben genannten Anwendung dar.In addition, the media according to the invention can also be used to produce holographic images or representations, for example for personal portraits, biometric representations in security documents, or generally images or image structures for advertising, security labels, brand protection, branding, labels, design elements, decorations, illustrations, trading cards , Pictures and the like as well as pictures which can represent digital data also in combination with the products shown above. Holographic images can have the impression of a three-dimensional image, but they can also represent image sequences, short films or a number of different objects, depending on the angle from which (also moving) light source, etc. it is illuminated. Due to these diverse design possibilities, holograms, especially volume holograms, represent an attractive technical solution for the above-mentioned application.

Weiterhin Gegenstand der vorliegenden Erfindung ist daher die Verwendung eines erfindungsgemäßen holographischen Mediums zur Aufzeichnung von In-Line, Off-Axis, Full-Aperture Transfer, Weißlicht-Transmissions, Denisyuk, Off-Axis Reflektions oder Edge-Lit Hologrammen sowie holographischen Stereogrammen, insbesondere zur Herstellung von optischen Elementen, Bildern oder Bilddarstellungen.The present invention therefore furthermore relates to the use of a holographic medium according to the invention for recording in-line, off-axis, full-aperture transfer, white light transmissions, Denisyuk, off-axis reflection or edge-lit holograms and holographic stereograms, in particular for Production of optical elements, pictures or picture representations.

Weiterhin Gegenstand der vorliegenden Erfindung ist auch ein Verfahren zur Herstellung eines holographischen Mediums unter Verwendung einer erfindungsgemäßen Photopolymer-Formulierung.The present invention furthermore also relates to a method for producing a holographic medium using a photopolymer formulation according to the invention.

Die Photopolymer-Formulierungen können insbesondere zur Herstellung holographischer Medien in Form eines Films verwendet werden. Dabei wird als Träger eine Lage eines für Licht im sichtbaren Spektralbereich (Transmission größer als 85% im Wellenlängenbereich von 400 bis 780 nm) transparenten Materials oder Materialverbunds ein- oder beidseitig beschichtet sowie ggf. eine Abdeckschicht auf der oder den Photopolymerlagen appliziert.The photopolymer formulations can be used in particular for the production of holographic media in the form of a film. In this case, a layer of a material or composite material that is transparent to light in the visible spectral range (transmission greater than 85% in the wavelength range from 400 to 780 nm) is coated on one or both sides and, if appropriate, a cover layer is applied to the photopolymer layer or layers.

Bevorzugte Materialien oder Materialverbünde des Trägers basieren auf Polycarbonat (PC), Polyethylenterephthalat (PET), Polybutylenterephthalat, Polyethylen, Polypropylen, Celluloseacetat, Cellulosehydrat, Cellulosenitrat, Cycloolefinpolymere, Polystyrol, Polyepoxide, Polysulfon, Cellulosetriacetat (CTA), Polyamid, Polymethylmethacrylat, Polyvinylchlorid, Polyvinylbutyral oder Polydicyclopentadien oder deren Mischungen. Besonders bevorzugt basieren sie auf PC, PET und CTA. Materialverbünde können Folienlaminate oder Coextrudate sein. Bevorzugte Materialverbünde sind Duplex- und Triplexfolien aufgebaut nach einem der Schemata A/B, A/B/A oder A/B/C. Besonders bevorzugt sind PC/PET, PET/PC/PET und PC/TPU (TPU = Thermoplastisches Polyurethan).Preferred materials or material composites of the carrier are based on polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene, polypropylene, cellulose acetate, cellulose hydrate, cellulose nitrate, cycloolefin polymers, polystyrene, polyepoxide, polysulfone, cellulose triacetate (CTA), polyamide, polyvinyl chloride, polyamide, polyvinyl chloride, polyamide, polyvinyl chloride, polyamide, polyvinyl chloride, polyamide, polyvinyl chloride, polyamide, polyvinyl chloride or polydicyclopentadiene or mixtures thereof. They are particularly preferably based on PC, PET and CTA. Composite materials can be film laminates or coextrudates. Preferred material composites are duplex and triplex films constructed according to one of the schemes A / B, A / B / A or A / B / C. PC / PET, PET / PC / PET and PC / TPU (TPU = thermoplastic polyurethane) are particularly preferred.

Die Materialien oder Materialverbünde des Trägers können einseitig oder beidseitig antihaftend, antistatisch, hydrophobiert oder hydrophiliert ausgerüstet sein. Die genannten Modifikationen dienen an der Photopolymerschicht zugewandten Seite dem Zweck, dass die Photopolymerlage von dem Träger zerstörungsfrei abgelöst werden kann. Eine Modifikation der der Photopolymerlage abgewandten Seite des Trägers dient dazu, dass die erfindungsgemäßen Medien speziellen mechanischen Anforderungen genügen, die z.B. bei der Verarbeitung in Rollenlaminatoren, insbesondere bei Rolle-zu-Rolle-Verfahren, gefordert sind.The materials or material composites of the carrier can be provided with one-sided or double-sided anti-adhesive, antistatic, hydrophobic or hydrophilized. The modifications mentioned serve the purpose on the side facing the photopolymer layer so that the photopolymer layer can be detached from the support without destruction. A modification of the side of the support facing away from the photopolymer layer serves to ensure that the media according to the invention meet special mechanical requirements, which e.g. when processing in roll laminators, especially in roll-to-roll processes.

Die folgenden Beispiele dienen der beispielhaften Erläuterung der Erfindung.The following examples serve to illustrate the invention by way of example.

BeispieleExamples Messmethoden:Measurement methods: OH Zahl:OH number:

Die angegebenen OH-Zahlen wurden gemäß DIN 53240-2 bestimmt.The specified OH numbers were determined in accordance with DIN 53240-2.

NCO-Wert:NCO value:

Die angegebenen NCO-Werte (Isocyanat-Gehalte) wurden gemäß DIN EN ISO 11909 bestimmt.The stated NCO values (isocyanate contents) were determined in accordance with DIN EN ISO 11909.

Bestimmung der Beugungseffizienz bei Puls-Belichtung:Determination of the diffraction efficiency with pulse exposure:

Zur Bestimmung der Beugungseffizienz bei Puls-Belichtung wurde das Denisyuk Hologramm eines Spiegels in eine Probe, bestehend aus einer Glasplatte mit auflaminiertem Photopolymerfilm, aufgezeichnet. Das Substrat des Photopolymerfilms zeigte dabei zur Laserquelle und das Glassubstrat zum Spiegel. Die Probe war bei der Belichtung mit ihrer Planfläche senkrecht zum Laserstrahl ausgerichtet. Der Abstand Probe zum Spiegel betrug 3 cm.To determine the diffraction efficiency with pulse exposure, the Denisyuk hologram of a mirror was recorded in a sample consisting of a glass plate with a laminated photopolymer film. The substrate of the photopolymer film pointed to the laser source and the glass substrate to the mirror. When exposed, the sample was aligned with its flat surface perpendicular to the laser beam. The distance between sample and mirror was 3 cm.

Als Laser wurde ein Puls-Laser der Firma Quantel aus Frankreich, Modell Brilliant b, verwendet. Es handelte sich dabei um einen Q-switched Nd-YAG Laser mit einem Modul zur Frequenzverdopplung zu 532 nm. Der Single Frequency Mode wurde durch einen Seed Laser garantiert. Die rechnerische Kohärenzlänge betrug ca. 1 m. Die Pulsdauer 4 ns und die mittlere Ausgangsleistung 3 Watt bei einer Pulswiederholungsrate von 10 Hz.A pulse laser from the French company Quantel, model Brilliant b, was used as the laser. It was a Q-switched Nd-YAG laser with a module for frequency doubling to 532 nm. The single frequency mode was guaranteed by a seed laser. The calculated coherence length was approx. 1 m. The pulse duration 4 ns and the average output power 3 watts with a pulse repetition rate of 10 Hz.

Mit dem elektronisch geregelten Shutter wurde eine Einfachpulsbelichtung sichergestellt. Die Wellenplatte erlaubte die Rotation der Polarisationsebene des Laserlichts und mit dem darauffolgenden Polarisator wurde der S-polarisierte Anteil des Laserlichtes in Richtung der Probe reflektiert. Die Strahlaufweitung erlaubte die Einstellung der belichteten Fläche. Die Wellenplatte und die Strahlaufweitung wurden so eingestellt, dass die Probe eine Belichtungsdosis von 100 mJ/cm2/Puls erreichte.Single pulse exposure was ensured with the electronically controlled shutter. The wave plate allowed the rotation of the plane of polarization of the laser light and with the following polarizer the S-polarized portion of the laser light was reflected in the direction of the sample. The beam expansion allowed the setting of the exposed area. The wave plate and beam expansion were adjusted so that the sample reached an exposure dose of 100 mJ / cm 2 / pulse.

Zur Bestimmung der Beugungseffizienz wurden die Proben jeweils genau mit einem Puls belichtet. Nach der Belichtung wurde die Probe auf einem Leuchttisch geblichen.To determine the diffraction efficiency, the samples were each exposed precisely with a pulse. After exposure, the sample was bleached on a light table.

Durch das Hologramm der geblichenen Probe wurde ein Transmissionsspektrum gemessen. Es wurde ein Spektrometer der Firma Ocean Optics, Modell HR4000 verwendet. Die Probe wurde senkrecht zum Lichtstrahl gestellt. Das Transmissionsspektrum zeigte bei der Wellenlänge, bei der die Bragg-Bedingung erfüllt war, einen Einbruch der Transmission. Die Tiefe des Transmissionseinbruchs zur Basislinie wurde als Beugungseffizienz DE des Denisyuk Hologramms des Spiegels ausgewertet.A transmission spectrum was measured through the hologram of the bleached sample. A spectrometer from the company Ocean Optics, model HR4000 was used. The sample was placed perpendicular to the light beam. The transmission spectrum showed a drop in transmission at the wavelength at which the Bragg condition was met. The depth of the transmission dip to the baseline was evaluated as the diffraction efficiency DE of the Denisyuk hologram of the mirror.

Substanzen:Substances:

Die verwendeten Lösungsmittel wurden im Chemikalienhandel bezogen. Desmorapid Z Dibutylzinn-dilaurat [77-58-7], Produkt der Bayer MaterialScience AG, Leverkusen, Deutschland. Desmodur® N 3900 Produkt der Bayer MaterialScience AG, Leverkusen, DE, Hexandiisocyanat-basiertes Polyisocyanat, Anteil an Iminooxadiazindion mindestens 30 %, NCO-Gehalt: 23.5 %. Fomrez UL 28 Urethanisierungskatalysator, Handelsprodukt der Momentive Performance Chemicals, Wilton, CT, USA. Aluminiumchlorid [7446-70-0] ist bei Acros Organics, Geel, BE erhältlich. 1-Chloro-3,4-difluorobenzol [696-02-6] ist bei ABCR GmbH & CO. KG, Karlsruhe erhältlich. 1-Bromo-3,4-difluorobenzol [348-61-8] ist bei ABCR GmbH & CO. KG, Karlsruhe erhältlich. 1,4-Difluorbenzol [540-36-3] ist bei Aldrich Chemie, Steinheim erhältlich. 4-Chlorofluorobenzol [352-33-0] ist bei ABCR GmbH & CO. KG, Karlsruhe erhältlich. 4-Bromfluorbenzol [460-00-4] ist bei Aldrich Chemie, Steinheim erhältlich. 4-Chlorphenylmagnesiumbromid [873-77-8] ist als 0.9 M Lösung in THF/Toluol bei Aldrich Chemie, Steinheim erhältlich. 4-Fluorphenylmagnesiumbromid [352-13-6] ist als 1.0M Lösung in THF bei Aldrich Chemie, Steinheim erhältlich. Tetrabutylammoniumbromid [1643-19-2] ist bei ABCR GmbH & CO. KG, Karlsruhe erhältlich. Safranin O [10309-89-4] ist bei Chemos GmbH, Deutschland, Art.-Nr. 1308 erhältlich. Die Zusammensetzung des Substanzgemisches ist in EP 2450893 A1 beschrieben. Natrium-bis(2-ethylhexyl)-sulfosuccinat [45297-26-5] ist bei Aldrich Chemie, Steinheim erhältlich. The solvents used were obtained from the chemical trade. Desmorapid Z Dibutyltin dilaurate [77-58-7], product of Bayer MaterialScience AG, Leverkusen, Germany. Desmodur® N 3900 Product of Bayer MaterialScience AG, Leverkusen, DE, hexane diisocyanate-based polyisocyanate, iminooxadiazinedione content at least 30%, NCO content: 23.5%. Fomrez UL 28 Urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, CT, USA. Aluminum chloride [7446-70-0] is available from Acros Organics, Geel, BE. 1-chloro-3,4-difluorobenzene [696-02-6] is available from ABCR GmbH & CO. KG, Karlsruhe available. 1-bromo-3,4-difluorobenzene [348-61-8] is available from ABCR GmbH & CO. KG, Karlsruhe available. 1,4-difluorobenzene [540-36-3] is available from Aldrich Chemie, Steinheim. 4-chlorofluorobenzene [352-33-0] is at ABCR GmbH & CO. KG, Karlsruhe available. 4-bromofluorobenzene [460-00-4] is available from Aldrich Chemie, Steinheim. 4-chlorophenyl magnesium bromide [873-77-8] is available as a 0.9 M solution in THF / toluene from Aldrich Chemie, Steinheim. 4-fluorophenyl magnesium bromide [352-13-6] is available as a 1.0M solution in THF from Aldrich Chemie, Steinheim. Tetrabutylammonium bromide [1643-19-2] is at ABCR GmbH & CO. KG, Karlsruhe available. Safranin O [10309-89-4] is available from Chemos GmbH, Germany, item no. 1308 available. The composition of the mixture of substances is in EP 2450893 A1 described. Sodium bis (2-ethylhexyl) sulfosuccinate [45297-26-5] is available from Aldrich Chemie, Steinheim.

Verbindungen der Formel (I)Compounds of formula (I) Beispiel 1: 4-FluortrichlorbenzolExample 1: 4-fluorotrichlorobenzene

4-Fluortrichlorbenzol [402-42-6] ist bei ABCR GmbH & CO. KG, Karlsruhe erhältlich und wurde eingesetzt wie erhalten.4-fluorotrichlorobenzene [402-42-6] is available from ABCR GmbH & CO. KG, Karlsruhe available and was used as received.

Beispiel 2: Herstellung von 1,2,4-Trifluor-5-(trichlormethyl)benzol : Example 2: Preparation of 1,2,4-trifluoro-5- (trichloromethyl) benzene :

In einem 250 mL Vierhals-Rundkolben mit Rückfluss-Kühler, Tropftrichter, Innenthermometer und mechanischem Rührer wurden unter Stickstoff 20.7 g Aluminiumtrichlorid in 75 mL Tetrachlorkohlenstoff suspendiert. Zu dieser Suspension wurden 10.2 g 1,2,4-Trifluorbenzol langsam zugeben, so dass das Reaktionsgemisch sanft refluxierte. Das entstehende HCl-Gas wurde in wässrige Natronlauge eingeleitet. Nach beendeter Zugabe wurde 10 min nachgerührt und anschließend auf Raumtemperatur abgekühlt. Das Reaktionsgemisch wurde auf 300 mL Eiswasser ausgetragen und die organische Phase abgetrennt. Die organische Phase wurde einmal mit 100 mL Wasser, einmal mit 100 mL 5% NaHCO3-Lösung und erneut einmal mit 100 mL Wasser gewaschen. Der Tetrachlorkohlenstoff wurde abdestilliert und aus dem Öl kristallisierte das gewünschte Produkt (5.6 g) in Form farbloser feiner Nadeln aus.20.7 g of aluminum trichloride were suspended in 75 ml of carbon tetrachloride under nitrogen in a 250 ml four-necked round-bottomed flask with reflux condenser, dropping funnel, internal thermometer and mechanical stirrer. 10.2 g of 1,2,4-trifluorobenzene were slowly added to this suspension, so that the reaction mixture refluxed gently. The resulting HCl gas was introduced into aqueous sodium hydroxide solution. After the addition had ended, the mixture was stirred for a further 10 minutes and then cooled to room temperature. The reaction mixture was poured onto 300 ml of ice water and the organic phase was separated off. The organic phase was washed once with 100 mL water, once with 100 mL 5% NaHCO 3 solution and once again with 100 mL water. The carbon tetrachloride was distilled off and the desired product (5.6 g) crystallized from the oil in the form of colorless fine needles.

Beispiel 3: Herstellung von 1-Chlor-4,5-difluor-2-(trichlormethyl)benzol:Example 3: Preparation of 1-chloro-4,5-difluoro-2- (trichloromethyl) benzene:

In einem 250 mL Vierhals-Rundkolben mit Rückfluss-Kühler, Tropftrichter, Innenthermometer und mechanischem Rührer wurden unter Stickstoff 27.4 g Aluminiumtrichlorid in 100 mL Tetrachlorkohlenstoff suspendiert. Zu dieser Suspension wurden 15.3 g 1-Chlor-3,4-difluorobenzol langsam zugeben, so dass das Reaktionsgemisch sanft refluxierte. Das entstehende HCl-Gas wurde in wässrige Natronlauge eingeleitet. Nach beendeter Zugabe wurde 10 min nachgerührt und anschließend auf Raumtemperatur abgekühlt. Das Reaktionsgemisch wurde auf 300 mL Eiswasser ausgetragen und die organische Phase abgetrennt. Die organische Phase wurde einmal mit 100 mL Wasser, einmal mit 100 mL 5% NaHCO3-Lösung und erneut einmal mit 100 mL Wasser gewaschen. Der Tetrachlorkohlenstoff wurde abdestilliert und wenig Acetonitril zugesetzt. Aus dieser Lösung kristallisierte das gewünschte Produkt (6.0 g) in Form farbloser feiner Nadeln aus.27.4 g of aluminum trichloride were suspended in 100 ml of carbon tetrachloride in a 250 ml four-necked round-bottomed flask with a reflux condenser, dropping funnel, internal thermometer and mechanical stirrer. 15.3 g of 1-chloro-3,4-difluorobenzene were slowly added to this suspension, so that the reaction mixture refluxed gently. The resulting HCl gas was in introduced aqueous sodium hydroxide solution. After the addition had ended, the mixture was stirred for a further 10 minutes and then cooled to room temperature. The reaction mixture was poured onto 300 ml of ice water and the organic phase was separated off. The organic phase was washed once with 100 mL water, once with 100 mL 5% NaHCO 3 solution and once again with 100 mL water. The carbon tetrachloride was distilled off and a little acetonitrile was added. The desired product (6.0 g) crystallized from this solution in the form of colorless fine needles.

Beispiel 4: Herstellung von 5-Chlor-1,2-difluor-3-(trichlormethyl)benzol:Example 4: Preparation of 5-chloro-1,2-difluoro-3- (trichloromethyl) benzene:

Die Mutterlauge aus der Herstellung von Beispiel 3 wurde am Vakuum vom Acetonitril befreit und das verbliebene Öl (14.7 g) bestand aus dem isomeren 5-Chlor-1,2-difluor-3-(trichlormethyl)-benzol.The mother liquor from the preparation of Example 3 was freed from the acetonitrile in vacuo and the remaining oil (14.7 g) consisted of the isomeric 5-chloro-1,2-difluoro-3- (trichloromethyl) benzene.

Beispiel 5: Herstellung von 1-Brom-4,5-difluor-2-(trichlormethyl)benzol:Example 5: Preparation of 1-bromo-4,5-difluoro-2- (trichloromethyl) benzene:

In einem 250 mL Vierhals-Rundkolben mit Rückfluss-Kühler, Tropftrichter, Innenthermometer und mechanischem Rührer wurden unter Stickstoff 27.4 g Aluminiumtrichlorid in 100 mL Tetrachlorkohlenstoff suspendiert. Zu dieser Suspension wurden 19.8 g 1-Brom-3,4-difluorobenzol langsam zugeben, so dass das Reaktionsgemisch sanft refluxierte. Das entstehende HCl-Gas wurde in wässrige Natronlauge eingeleitet. Nach beendeter Zugabe wurde 10 min nachgerührt und anschließend auf Raumtemperatur abgekühlt. Das Reaktionsgemisch wurde auf 300 mL Eiswasser ausgetragen und die organische Phase abgetrennt. Die organische Phase wurde einmal mit 100 mL Wasser, einmal mit 100 mL 5% NaHCO3-Lösung und erneut einmal mit 100 mL Wasser gewaschen. Der Tetrachlorkohlenstoff wurde abdestilliert und wenig Acetonitril zugesetzt. Aus dieser Lösung kristallisierte das gewünschte Produkt (4.4 g) in Form farbloser feiner Nadeln aus.27.4 g of aluminum trichloride were suspended in 100 ml of carbon tetrachloride in a 250 ml four-necked round-bottomed flask with a reflux condenser, dropping funnel, internal thermometer and mechanical stirrer. 19.8 g of 1-bromo-3,4-difluorobenzene were slowly added to this suspension, so that the reaction mixture refluxed gently. The resulting HCl gas was introduced into aqueous sodium hydroxide solution. After the addition had ended, the mixture was stirred for a further 10 minutes and then cooled to room temperature. The reaction mixture was poured onto 300 ml of ice water and the organic phase was separated off. The organic phase was washed once with 100 mL water, once with 100 mL 5% NaHCO 3 solution and once again with 100 mL water. The carbon tetrachloride was distilled off and a little acetonitrile was added. The desired product (4.4 g) crystallized from this solution in the form of colorless fine needles.

Beispiel 6: Herstellung von 5-Brom-1,2-difluor-3-(trichlormethyl)benzol:Example 6: Preparation of 5-bromo-1,2-difluoro-3- (trichloromethyl) benzene:

Die Mutterlauge aus der Herstellung von Beispiel 5 wurde am Vakuum vom Acetonitril befreit und das verbliebene Öl (22.0 g) bestand aus dem isomeren 5-Brom-1,2-difluor-3-(trichlormethyl)-benzol.The mother liquor from the preparation of Example 5 was freed from the acetonitrile in vacuo and the remaining oil (22.0 g) consisted of the isomeric 5-bromo-1,2-difluoro-3- (trichloromethyl) benzene.

Beispiel 7: Herstellung von 1,4-Difluor-2-(trichlormethyl)benzol:Example 7: Preparation of 1,4-difluoro-2- (trichloromethyl) benzene:

In einem 250 mL Vierhals-Rundkolben mit Rückfluss-Kühler, Tropftrichter, Innenthermometer und mechanischem Rührer wurden unter Stickstoff 27.4 g Aluminiumtrichlorid in 100 mL Tetrachlorkohlenstoff suspendiert. Zu dieser Suspension wurden 11.7 g 1,4-Difluorobenzol langsam zugeben, so dass das Reaktionsgemisch sanft refluxierte. Das entstehende HCl-Gas wurde in wässrige Natronlauge eingeleitet. Nach beendeter Zugabe wurde 10 min nachgerührt und anschließend auf Raumtemperatur abgekühlt. Das Reaktionsgemisch wurde auf 300 mL Eiswasser ausgetragen und die organische Phase abgetrennt. Die organische Phase wurde einmal mit 100 mL Wasser, einmal mit 100 mL 5% NaHCO3-Lösung und erneut einmal mit 100 mL Wasser gewaschen. Der Tetrachlorkohlenstoff wurde abdestilliert und wenig Acetonitril zugesetzt. Aus dieser Lösung kristallisierte das gewünschte Produkt (8.0 g) in Form farbloser feiner Nadeln aus.27.4 g of aluminum trichloride were suspended in 100 ml of carbon tetrachloride in a 250 ml four-necked round-bottomed flask with a reflux condenser, dropping funnel, internal thermometer and mechanical stirrer. 11.7 g of 1,4-difluorobenzene were slowly added to this suspension, so that the reaction mixture refluxed gently. The resulting HCl gas was introduced into aqueous sodium hydroxide solution. After the addition had ended, the mixture was stirred for a further 10 minutes and then cooled to room temperature. The reaction mixture was poured onto 300 ml of ice water and the organic phase was separated off. The organic phase was washed once with 100 mL water, once with 100 mL 5% NaHCO 3 solution and once again with 100 mL water. The carbon tetrachloride was distilled off and a little acetonitrile was added. The desired product (8.0 g) crystallized from this solution in the form of colorless fine needles.

Beispiel 8: Herstellung von 1-Chlor-4-fluor-2-(trichlormethyl)benzol und 4-Chlor-1-fluor-2-(trichlormethyl)benzol : Example 8: Preparation of 1-chloro-4-fluoro-2- (trichloromethyl) benzene and 4-chloro-1-fluoro-2- (trichloromethyl) benzene :

In einem 250 mL Vierhals-Rundkolben mit Rückfluss-Kühler, Tropftrichter, Innenthermometer und mechanischem Rührer wurden unter Stickstoff 27.4 g Aluminiumtrichlorid in 100 mL Tetrachlorkohlenstoff suspendiert. Zu dieser Suspension wurden 13.4 g 4-Chlorofluorobenzol langsam zugeben, so dass das Reaktionsgemisch sanft refluxierte. Das entstehende HCl-Gas wurde in wässrige Natronlauge eingeleitet. Nach beendeter Zugabe wurde 10 min nachgerührt und anschließend auf Raumtemperatur abgekühlt. Das Reaktionsgemisch wurde auf 300 mL Eiswasser ausgetragen und die organische Phase abgetrennt. Die organische Phase wurde einmal mit 100 mL Wasser, einmal mit 100 mL 5% NaHCO3-Lösung und erneut einmal mit 100 mL Wasser gewaschen. Der Tetrachlorkohlenstoff wurde abdestilliert und wenig Acetonitril zugesetzt. Aus dieser Lösung fiel eine Mischung der gewünschte Produkte 1,4-Difluor-2-(trichlormethyl)benzol und 4-Chlor-1-fluor-2-(trichlormethyl)benzol (17.5 g) im Verhältnis von ca. 3:1 aus.27.4 g of aluminum trichloride were suspended in 100 ml of carbon tetrachloride in a 250 ml four-necked round-bottomed flask with a reflux condenser, dropping funnel, internal thermometer and mechanical stirrer. 13.4 g of 4-chlorofluorobenzene were slowly added to this suspension, so that the reaction mixture refluxed gently. The resulting HCl gas was introduced into aqueous sodium hydroxide solution. After the addition had ended, the mixture was stirred for a further 10 minutes and then cooled to room temperature. The reaction mixture was poured onto 300 ml of ice water and the organic phase was separated off. The organic phase was washed once with 100 mL water, once with 100 mL 5% NaHCO 3 solution and once again with 100 mL water. The carbon tetrachloride was distilled off and a little acetonitrile was added. From this solution, a mixture of the desired products 1,4-difluoro-2- (trichloromethyl) benzene and 4-chloro-1-fluoro-2- (trichloromethyl) benzene (17.5 g) precipitated in a ratio of approx. 3: 1.

Beispiel 9: Herstellung von 1,4-Difluor-2-(trichlormethyl)benzol:Example 9: Preparation of 1,4-difluoro-2- (trichloromethyl) benzene:

In einem 250 mL Vierhals-Rundkolben mit Rückfluss-Kühler, Tropftrichter, Innenthermometer und mechanischem Rührer wurden unter Stickstoff 27.4 g Aluminiumtrichlorid in 100 mL Tetrachlorkohlenstoff suspendiert. Zu dieser Suspension wurden 18.0 g 4-Bromfluorbenzol langsam zugeben, so dass das Reaktionsgemisch sanft refluxierte. Das entstehende HCl-Gas wurde in wässrige Natronlauge eingeleitet. Nach beendeter Zugabe wurde 10 min nachgerührt und anschließend auf Raumtemperatur abgekühlt. Das Reaktionsgemisch wurde auf 300 mL Eiswasser ausgetragen und die organische Phase abgetrennt. Die organische Phase wurde einmal mit 100 mL Wasser, einmal mit 100 mL 5% NaHCO3-Lösung und erneut einmal mit 100 mL Wasser gewaschen. Der Tetrachlorkohlenstoff wurde abdestilliert und wenig Acetonitril zugesetzt. Aus dieser Lösung kristallisierte das gewünschte Produkt (4.6 g) in Form farbloser feiner Nadeln aus.27.4 g of aluminum trichloride were suspended in 100 ml of carbon tetrachloride in a 250 ml four-necked round-bottomed flask with a reflux condenser, dropping funnel, internal thermometer and mechanical stirrer. 18.0 g of 4-bromofluorobenzene were slowly added to this suspension, so that the reaction mixture refluxed gently. The resulting HCl gas was introduced into aqueous sodium hydroxide solution. After the addition had ended, the mixture was stirred for 10 min and then opened Cooled to room temperature. The reaction mixture was poured onto 300 ml of ice water and the organic phase was separated off. The organic phase was washed once with 100 mL water, once with 100 mL 5% NaHCO 3 solution and once again with 100 mL water. The carbon tetrachloride was distilled off and a little acetonitrile was added. The desired product (4.6 g) crystallized from this solution in the form of colorless fine needles.

Herstellung der weiteren Komponenten für die Photopolymer-Formulierung:Production of the further components for the photopolymer formulation: Herstellung von Polyol 1:Production of polyol 1:

In einem 1 L Kolben wurden 0.18 g Zinnoctoat, 374.8 g ε-Caprolacton und 374.8 g eines difunktionellen Polytetrahydrofuranpolyetherpolyols (Equivalentgewicht 500 g/Mol OH) vorgelegt und auf 120 °C aufgeheizt und so lange auf dieser Temperatur gehalten, bis der Festgehalt (Anteil der nicht-flüchtigen Bestandteile) bei 99.5 Gew.-% oder darüber lag. Anschließend wurde abgekühlt und das Produkt als wachsiger Feststoff erhalten.0.18 g of tin octoate, 374.8 g of ε-caprolactone and 374.8 g of a difunctional polytetrahydrofuran polyether polyol (equivalent weight 500 g / mol OH) were placed in a 1 L flask and heated to 120 ° C. and kept at this temperature until the solids content (proportion of non-volatile constituents) was 99.5% by weight or above. It was then cooled and the product obtained as a waxy solid.

Herstellung des Urethanacrylats 1 (Schreibmonomer): Phosphorothioyltris(oxybenzol-4,1-diylcarbamoyloxyethan-2,1-diyl)trisacrylatPreparation of urethane acrylate 1 (writing monomer): phosphorothioyl tris (oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate

In einem 500 mL Rundkolben wurden 0.1 g 2,6-Di-tert.-butyl-4-methylphenol, 0.05 g Dibutylzinn-dilaurat sowie und 213.07 g einer 27 %-igen Lösung von Tris(p-isocyanatophenyl)thiophosphat in Ethylacetat (Desmodur® RFE, Produkt der Bayer MaterialScience AG, Leverkusen, Deutschland) vorgelegt und auf 60 °C erwärmt. Anschließend wurden 42.37 g 2-Hydroxyethylacrylat zugetropft und die Mischung weiter auf 60 °C gehalten, bis der Isocyanatgehalt unter 0.1 % gesunken war. Danach wurde abgekühlt und das Ethylacetat im Vakuum vollständig entfernt. Das Produkt wurde als teilkristalliner Feststoff erhalten.0.1 g of 2,6-di-tert-butyl-4-methylphenol, 0.05 g of dibutyltin dilaurate and 213.07 g of a 27% solution of tris (p-isocyanatophenyl) thiophosphate in ethyl acetate (Desmodur ® RFE, product of Bayer MaterialScience AG, Leverkusen, Germany) and heated to 60 ° C. Then 42.37 g of 2-hydroxyethyl acrylate were added dropwise and the mixture was kept at 60 ° C. until the isocyanate content had dropped below 0.1%. The mixture was then cooled and the ethyl acetate was removed completely in vacuo. The product was obtained as a semi-crystalline solid.

Herstellung des Urethanacrylats 2 (Schreibmonomer): 2-({[3-(Methylsulfanyl)phenyl]-carbamoyl}oxy)ethylprop-2-enoatPreparation of urethane acrylate 2 (writing monomer): 2 - ({[3- (methylsulfanyl) phenyl] carbamoyl} oxy) ethylprop-2-enoate

In einem 100 mL Rundkolben wurden 0.02 g 2,6-Di-tert.-butyl-4-methylphenol, 0.01 g Desmorapid Z, 11.7 g 3-(Methylthio)phenylisocyanat [28479-1-8] vorgelegt und auf 60 °C erwärmt. Anschließend wurden 8.2 g 2-Hydroxyethylacrylat zugetropft und die Mischung weiter auf 60 °C gehalten, bis der Isocyanatgehalt unter 0.1 % gesunken war. Danach wurde abgekühlt. Das Produkt wurde als farblose Flüssigkeit erhalten.0.02 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of Desmorapid Z, 11.7 g of 3- (methylthio) phenyl isocyanate [28479-1-8] were placed in a 100 mL round-bottomed flask and heated to 60.degree . 8.2 g of 2-hydroxyethyl acrylate were then added dropwise and the mixture was further heated to 60.degree held until the isocyanate content had dropped below 0.1%. It was then cooled. The product was obtained as a colorless liquid.

Herstellung des Additivs 1 Bis(2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorheptyl)-(2,2,4-trimethylhexan-1,6-diyl)biscarbamatPreparation of additive 1 bis (2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) - (2,2,4-trimethylhexane-1,6-diyl) biscarbamate

In einem 50 mL Rundkolben wurden 0.02 g Desmorapid Z und 3.6 g 2,4,4-Trimethylhexane-1,6-diisocyanat (TMDI) vorgelegt und auf 60 °C erwärmt. Anschließend wurden 11.9 g 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluorheptan-1-ol zugetropft und die Mischung weiter auf 60 °C gehalten, bis der Isocyanatgehalt unter 0.1 % gesunken war. Danach wurde abgekühlt. Das Produkt wurde als farbloses Öl erhalten.0.02 g of Desmorapid Z and 3.6 g of 2,4,4-trimethylhexane-1,6-diisocyanate (TMDI) were placed in a 50 mL round-bottomed flask and heated to 60 ° C. 11.9 g of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorheptan-1-ol were then added dropwise and the mixture was kept at 60 ° C. until the isocyanate content was below 0.1%. had sunk. It was then cooled. The product was obtained as a colorless oil.

Herstellung des Borates 1 (Photoinitiator): Tetrabutylammonium-tris(4-chlorphenyl)(hexyl)boratPreparation of borate 1 (photoinitiator): tetrabutylammonium tris (4-chlorophenyl) (hexyl) borate

Zu einer Lösung von 15.4 g Dibrom-hexylboran*dimethylsulfid [64770-04-3] (hergestellt wie im Journal of the American Chemical Society (1977), 99, 7097-8 beschrieben) in 25 mL Toluol wurden bei 0 °C 72 mL einer 0.9 M Lösung von 4-Chlorphenylmagnesiumbromid [873-77-8] in THF/Toluol langsam zugetropft. Das Reaktionsgemisch wurde innerhalb 30 min auf Raumtemperatur erwärmt und anschließend für 2 h am Rückfluss erhitzt. Anschließend wurde das Lösungsmittel im Vakuum entfernt und der ölige Rest in 400 mL Methanol/Wasser (4:1) gelöst und vom ausgefallenen Feststoff filtriert. Die erhaltene Lösung wurde mit 15.6 g Tetrabutylammoniumbromid versetzt und der ausgefallene Feststoff wurde durch Filtration isoliert und im Vakuum getrocknet. Man erhielt 12.2 g eines farblosen Feststoffes.To a solution of 15.4 g dibromo-hexylborane * dimethyl sulfide [64770-04-3] (prepared as in Journal of the American Chemical Society (1977), 99, 7097-8 described) in 25 mL toluene, 72 mL of a 0.9 M solution of 4-chlorophenylmagnesium bromide [873-77-8] in THF / toluene were slowly added dropwise at 0 ° C. The reaction mixture was warmed to room temperature within 30 min and then refluxed for 2 h. The solvent was then removed in vacuo and the oily residue was dissolved in 400 ml of methanol / water (4: 1) and the precipitated solid was filtered off. 15.6 g of tetrabutylammonium bromide were added to the solution obtained and the precipitated solid was isolated by filtration and dried in vacuo. 12.2 g of a colorless solid were obtained.

Herstellung des Borates 2 (Photoinitiator): Tetrabutylammonium-tris(4-fluorphenyl)(hexyl)boratPreparation of borate 2 (photoinitiator): tetrabutylammonium tris (4-fluorophenyl) (hexyl) borate

Zu einer Lösung von 12.5 g Dibrom-hexylboran*dimethylsulfid [64770-04-3] (hergestellt wie im Journal of the American Chemical Society (1977), 99, 7097-8 beschrieben) in 25 mL Toluol wurden bei 0 °C 60 mL einer 1.0 M Lösung von 4-Fluorphenylmagnesiumbromid [873-77-8] in THF langsam zugetropft. Das Reaktionsgemisch wurde innerhalb 30 min auf Raumtemperatur erwärmt und anschließend für 2 h am Rückfluss erhitzt. Anschließend wurde das Lösungsmittel im Vakuum entfernt und der ölige Rest in 400 mL Methanol/Wasser (4:1) gelöst und vom ausgefallenen Feststoff filtriert. Die erhaltene Lösung wurde mit 12.6 g Tetrabutylammoniumbromid versetzt und der ausgefallene Feststoff wurde durch Filtration isoliert und im Vakuum getrocknet. Man erhielt 10.2 g eines farblosen Feststoffes.To a solution of 12.5 g dibromo-hexylborane * dimethyl sulfide [64770-04-3] (prepared as in Journal of the American Chemical Society (1977), 99, 7097-8 60 mL of a 1.0 M solution of 4-fluorophenylmagnesium bromide [873-77-8] in THF were slowly added dropwise in 25 mL toluene at 0 ° C. The reaction mixture was warmed to room temperature within 30 min and then refluxed for 2 h. The solvent was then removed in vacuo removed and the oily residue dissolved in 400 mL methanol / water (4: 1) and filtered from the precipitated solid. The solution obtained was mixed with 12.6 g of tetrabutylammonium bromide and the precipitated solid was isolated by filtration and dried in vacuo. 10.2 g of a colorless solid were obtained.

Herstellung des Farbstoffs 1:Preparation of Dye 1:

5.07 g wasserfreies Natrium-bis(2-ethylhexyl)sulfosuccinat [45297-26-5] wurden in 50 mL wasserfreiem Essigsäureethylester gelöst. 4.00 g des wasserfreien Farbstoffs Safranin O [10309-89-4], Zusammensetzung siehe EP 2450893 A1 , wurden zugesetzt. Die Mischung wurde 3 h bei Raumtemperatur gerührt und über einen Faltenfilter filtriert. Nach Entfernen des Lösungsmittels im Vakuum erhielt 5.1 g des Farbstoffs Safranin O bis(2-ethylhexyl)sulfosuccinat [1374689-68-5] als hochviskoses Öl.5.07 g of anhydrous sodium bis (2-ethylhexyl) sulfosuccinate [45297-26-5] were dissolved in 50 mL of anhydrous ethyl acetate. 4.00 g of the anhydrous dye Safranin O [10309-89-4], composition see EP 2450893 A1 were added. The mixture was stirred at room temperature for 3 h and filtered through a pleated filter. After removing the solvent in vacuo, 5.1 g of the dye safranin O bis (2-ethylhexyl) sulfosuccinate [1374689-68-5] was obtained as a highly viscous oil.

Herstellung der Medien zur Bestimmung der holographischen EigenschaftenProduction of the media for determining the holographic properties Beispiel-Medium IExample medium I

3.38 g der Polyol-Komponente 1 wurden mit 0.010 g Beispiel 1, 2.00 g Urethanacrylat 1, 2.00 g Urethanacrylat 2, 1.50 g Additiv 1, 0.10 g Borat 1, 0.010 g Farbstoff 1 und 0.35 g N-Ethylpyrrolidon bei 60 °C gemischt, so dass eine klare Lösung erhalten wurde. Anschließend wurde auf 30 °C abgekühlt, 0.65 g Desmodur® N3900 zugegeben und erneut gemischt. Schließlich wurden 0.01 g Fomrez UL 28 zugegeben und erneut kurz gemischt. Die erhaltene, flüssige Masse wurde dann auf eine Glasplatte gegeben und dort mit einer zweiten Glasplatte abgedeckt. Dieser Probenkörper wurde 12 Stunden bei Raumtemperatur liegen gelassen und gehärtet.3.38 g of polyol component 1 were mixed with 0.010 g of example 1, 2.00 g of urethane acrylate 1, 2.00 g of urethane acrylate 2, 1.50 g of additive 1, 0.10 g of borate 1, 0.010 g of dye 1 and 0.35 g of N-ethylpyrrolidone at 60 ° C. so that a clear solution was obtained. The mixture was then cooled to 30 ° C., 0.65 g of Desmodur® N3900 was added and the mixture was mixed again. Finally 0.01 g of Fomrez UL 28 was added and mixed again briefly. The liquid mass obtained was then placed on a glass plate and covered there with a second glass plate. This specimen was left at room temperature for 12 hours and cured.

Beispiel-Medium IIExample medium II

Es wurde gearbeitet wie im Beispiel Medium I, aber unter Verwendung von 0.10 g Borat 2 anstatt 0.10 g Borat 1.The procedure was as in Example Medium I, but using 0.10 g borate 2 instead of 0.10 g borate 1.

Beispiel-Medium IIIExample medium III

Es wurde gearbeitet wie im Beispiel Medium I, aber unter Verwendung von 0.010 g Beispiel 2 anstatt 0.010 g Beispiel 1.The procedure was as in Example Medium I, but using 0.010 g of Example 2 instead of 0.010 g of Example 1.

Beispiel-Medium IVExample medium IV

Es wurde gearbeitet wie im Beispiel Medium I, aber unter Verwendung von 0.010 g Beispiel 3 anstatt 0.010 g Beispiel 1 sowie unter Verwendung von 0.10 g Borat 2 anstatt 0.10 g Borat 1.The procedure was as in Example Medium I, but using 0.010 g of Example 3 instead of 0.010 g of Example 1 and using 0.10 g of Borate 2 instead of 0.10 g of Borate 1.

Beispiel-Medium VExample medium V

Es wurde gearbeitet wie im Beispiel Medium I, aber unter Verwendung von 0.010 g Beispiel 4 anstatt 0.010 g Beispiel 1.The procedure was as in Example Medium I, but using 0.010 g of Example 4 instead of 0.010 g of Example 1.

Beispiel-Medium VIExample medium VI

Es wurde gearbeitet wie im Beispiel Medium I, aber unter Verwendung von 0.010 g Beispiel 5 anstatt 0.010 g Beispiel 1.The procedure was as in Example Medium I, but using 0.010 g of Example 5 instead of 0.010 g of Example 1.

Beispiel-Medium VIIExample medium VII

Es wurde gearbeitet wie im Beispiel Medium I, aber unter Verwendung von 0.010 g Beispiel 6 anstatt 0.010 g Beispiel 1.The procedure was as in Example Medium I, but using 0.010 g of Example 6 instead of 0.010 g of Example 1.

Beispiel-Medium VIIIExample medium VIII

Es wurde gearbeitet wie im Beispiel Medium I, aber unter Verwendung von 0.010 g Beispiel 7 anstatt 0.010 g Beispiel 1 sowie unter Verwendung von 0.10 g Borat 2 anstatt 0.10 g Borat 1.The procedure was as in Example Medium I, but using 0.010 g of Example 7 instead of 0.010 g of Example 1 and using 0.10 g of Borate 2 instead of 0.10 g of Borate 1.

Beispiel-Medium IXExample medium IX

Es wurde gearbeitet wie im Beispiel Medium I, aber unter Verwendung von 0.010 g Beispiel 8 anstatt 0.010 g Beispiel 1 sowie unter Verwendung von 0.10 g Borat 2 anstatt 0.10 g Borat 1.The procedure was as in Example Medium I, but using 0.010 g of Example 8 instead of 0.010 g of Example 1 and using 0.10 g of Borate 2 instead of 0.10 g of Borate 1.

Beispiel-Medium XExample medium X

Es wurde gearbeitet wie im Beispiel Medium I, aber unter Verwendung von 0.010 g Beispiel 9 anstatt 0.010 g Beispiel 1.The procedure was as in Example Medium I, but using 0.010 g Example 9 instead of 0.010 g Example 1.

Vergleichs-Medium V-1Comparative medium V-1

3.38 g der Polyol-Komponente 1 wurden mit 2.00 g Urethanacrylat 1, 2.00 g Urethanacrylat 2, 1.50 g Additiv 1, 0.10 g Borat 1, 0.010 g Farbstoff 1 und 0.35 g N-Ethylpyrrolidon bei 60 °C gemischt, so dass eine klare Lösung erhalten wurde. Anschließend wurde auf 30 °C abgekühlt, 0.65 g Desmodur® N3900 zugegeben und erneut gemischt. Schließlich wurden 0.01 g Fomrez UL 28 zugegeben und erneut kurz gemischt. Die erhaltene, flüssige Masse wurde dann auf eine Glasplatte gegeben und dort mit einer zweiten Glasplatte abgedeckt. Dieser Probenkörper wurde 12 Stunden bei Raumtemperatur liegen gelassen und gehärtet.3.38 g of polyol component 1 were mixed with 2.00 g of urethane acrylate 1, 2.00 g of urethane acrylate 2, 1.50 g of additive 1, 0.10 g of borate 1, 0.010 g of dye 1 and 0.35 g of N-ethylpyrrolidone at 60 ° C., so that a clear solution was obtained. The mixture was then cooled to 30 ° C., 0.65 g of Desmodur® N3900 was added and the mixture was mixed again. Finally 0.01 g of Fomrez UL 28 was added and mixed again briefly. The liquid mass obtained was then placed on a glass plate and covered there with a second glass plate. This specimen was left at room temperature for 12 hours and cured.

Vergleichs-Medium V-2Comparative medium V-2

Es wurde gearbeitet wie im Vergleichs-Medium V-1, aber unter Verwendung von 0.10 g Borat 2 anstatt 0.10 g Borat 1.The procedure was as in comparison medium V-1, but using 0.10 g borate 2 instead of 0.10 g borate 1.

Holographische Prüfung:Holographic check:

Die wie beschrieben hergestellten Medien wurden mittels einer Messordnung gemäß Figur 1 in der oben beschriebenen Weise (Bestimmung der Beugungseffizienz bei Puls-Belichtung) auf ihre holographischen Eigenschaften geprüft. Dabei ergaben sich folgende Messwerte für DE bei einer fixen Dosis 100 mJ/cm2: Tab. 1: Holographische Bewertung ausgewählter Beispiele Beispiel-Medium Beispiel gemäß Formel (I) Borat Single pulse DE [%] I 1 1 22 II 1 2 21 III 2 1 38 IV 3 2 37 V 4 1 29 VI 5 1 34 VII 6 1 19 VIII 7 2 24 IX 8 2 26 X 9 1 27 Tab. 2: Holographische Bewertung ausgewählter Vergleichs-Medien Vergleichs-Medium Additiv Borat Single pulse DE [%] V-1 - 1 - V-2 - 2 - The media produced as described were measured using a measurement order Figure 1 tested for their holographic properties in the manner described above (determination of the diffraction efficiency with pulse exposure). The following measured values for DE resulted at a fixed dose of 100 mJ / cm 2 : Tab. 1: Holographic evaluation of selected examples Example medium Example according to formula (I) Borate Single pulse DE [%] I. 1 1 22 II 1 2nd 21 III 2nd 1 38 IV 3rd 2nd 37 V 4th 1 29 VI 5 1 34 VII 6 1 19th VIII 7 2nd 24th IX 8th 2nd 26 X 9 1 27 Comparison medium Additive Borate Single pulse DE [%] V-1 - 1 - V-2 - 2nd -

Die gefundenen Werte für die Beispiel-Medien I bis X zeigen, dass die in den Photopolymer-Formulierungen eingesetzten erfindungsgemäßen Verbindungen der Formel (I) für die Verwendung in holographischen Medien bei Belichtung mit gepulstem Laser sehr gut geeignet sind. Die Vergleichs-Medien V-1 und V-2 weisen keine erfindungsgemäßen Verbindung der Formel (I) auf und sind für die Verwendung in holographischen Medien bei Belichtung mit gepulstem Laser ungeeignet. The values found for the example media I to X show that the compounds of the formula (I) according to the invention used in the photopolymer formulations are very well suited for use in holographic media when exposed to a pulsed laser. The comparison media V-1 and V-2 have no compound of the formula (I) according to the invention and are unsuitable for use in holographic media when exposed to a pulsed laser.

Claims (15)

  1. Photopolymer formulation comprising matrix polymers, a writing monomer and a photoinitiator, characterized in that it further comprises a compound of formula (I)
    Figure imgb0007
     where
    A1, A2 and A3 are each independently hydrogen, fluorine, chlorine, bromine or iodine,
    R1, R2, R3, R4 and R5 are each independently hydrogen, halogen, cyano, nitro, isonitrile, acyl, carboxyl, carboxylic ester, carboxamide, orthoester, sulphonate, phosphate, organosulphonyl, organosulphoxidyl, optionally fluorinated alkoxy and preferably hydrogen, halogen, cyano, nitro, isonitrile, acyl, carboxyl, further preferably hydrogen, halogen and particularly preferably hydrogen, fluorine, chlorine, bromine or iodine and suitable radicals may be connected together via a bridge of any desired substitution, or in that two or more compounds of formula (I) may be connected together via at least one of the radicals R1, R2, R3, R4 and R5 , in which case these radicals therein constitute a 2- to 4-ply functional bridge, with the proviso that at least one of the radicals R1, R2, R3, R4 and R5 is not hydrogen.
  2. Photopolymer formulation according to Claim 1, characterized in that A1, A2 and A3 are each independently fluorine, chlorine, bromine or iodine and preferably A1, A2 and A3 are all either fluorine, chlorine, bromine or iodine.
  3. Photopolymer formulation according to any of Claims 1 to 2, characterized in that the matrix polymers are in a crosslinked and preferably three-dimensionally crosslinked state.
  4. Photopolymer formulation according to any of Claims 1 to 3, characterized in that the matrix polymers are polyurethanes.
  5. Photopolymer formulation according to Claim 4, characterized in that the polyurethanes are obtainable by reacting at least one polyisocyanate component with at least one isocyanate-reactive component.
  6. Photopolymer comprising matrix polymers, a writing monomer and a photoinitiator, characterized in that it further comprises a compound of formula (I)
    Figure imgb0008
     where
    A1, A2 and A3 are each independently hydrogen, fluorine, chlorine, bromine or iodine,
    R1, R2, R3, R4 and R5 are each independently hydrogen, halogen, cyano, nitro,, isonitrile, acyl, carboxyl, carboxylic ester, carboxamide, orthoester, sulphonate, phosphate, organosulphonyl, organosulphoxidyl, optionally fluorinated alkoxy and preferably hydrogen, halogen, cyano, nitro, isonitrile, acyl, carboxyl, further preferably hydrogen, halogen and particularly preferably hydrogen, fluorine, chlorine, bromine or iodine and suitable radicals may be connected together via a bridge of any desired substitution, or in that two or more compounds of formula (I) may be connected together via at least one of the radicals R1, R2, R3, R4 and R5, in which case these radicals therein constitute a 2- to 4-ply functional bridge, with the proviso that at least one of the radicals R1, R2, R3, R4 and R5 is not hydrogen.
  7. Photopolymer according to Claim 6, characterized in that A1, A2 and A3 are each independently fluorine, chlorine, bromine or iodine and more preferably A1, A2 and A3 are all either fluorine, chlorine, bromine or iodine.
  8. Photopolymer according to any of Claims 6 to 7, characterized in that the matrix polymers are in a crosslinked and preferably three-dimensionally crosslinked state.
  9. Photopolymer according to any of Claims 6 to 8, characterized in that the matrix polymers are polyurethanes.
  10. Photopolymer according to Claim 9, characterized in that the polyurethanes are obtainable by reaction of at least one polyisocyanate component with at least one isocyanate-reactive component.
  11. Holographic medium, in particular in the form of a film, comprising a photopolymer according to at least one of Claims 6 to 10.
  12. Holographic medium according to Claim 11, characterized in that holographic information has been exposed.
  13. Use of a holographic medium according to Claim 11 for recording of in-line, off-axis, full-aperture transfer, white light transmission, reflection, Denisyuk, off-axis reflection or edge-lit holograms and also of holographic stereograms, in particular for production of optical elements, images or image depictions.
  14. Process for producing a holographic medium according to Claim 11, wherein a carrier of a material or material composite transparent to light within the visible spectral range is coated on one or both sides with a photopolymer formulation according to at least one of Claims 1 to 5, and a cover layer is preferably applied to the photopolymer ply or plies.
  15. Use of a photopolymer formulation according to any of Claims 1 to 5 for production of holographic media.
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Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180180994A1 (en) 2015-06-23 2018-06-28 Covestro Deutschland Ag Substituted triazines
JP6952113B2 (en) * 2016-11-09 2021-10-20 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ Method for producing triaryl organoborate
EP3538534B1 (en) 2016-11-09 2020-09-16 Covestro Intellectual Property GmbH & Co. KG Process for the manufacturing of triaryl-alkyl borates
WO2018099698A1 (en) 2016-11-09 2018-06-07 Covestro Deutschland Ag Process for the manufacturing of triarvl-organo borates
TW201906882A (en) 2017-05-09 2019-02-16 德商科思創德意志股份有限公司 Film structure containing a photopolymer layer for holographic illumination and a highly resistant lacquer layer
KR20200006988A (en) 2017-05-09 2020-01-21 코베스트로 도이칠란트 아게 System consisting of two dry-applicable UV-curable lacquer layers for protection of holograms in photopolymer film composites
EP3401910A1 (en) 2017-05-09 2018-11-14 Covestro Deutschland AG Holographic medium containing a photopolymeric coating for holographic exposure and a lacquer layer with high resistance
JP2020519943A (en) 2017-05-09 2020-07-02 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ Holographic media containing a photopolymer layer and a highly resistant coating layer for holographic exposure
TW201906730A (en) 2017-05-09 2019-02-16 德商科思創德意志股份有限公司 Plastic film containing UV curable adhesive layer for protecting the hologram in the photopolymer film composite
EP3401909A1 (en) 2017-05-09 2018-11-14 Covestro Deutschland AG Film structure comprising a photopolymer coating for holographic exposure and a lacquer layer with high resistance
EP3435156A1 (en) 2017-07-26 2019-01-30 Covestro Deutschland AG Protective layer for photopolymer
KR102166846B1 (en) * 2017-12-11 2020-10-16 주식회사 엘지화학 Photopolymer composition
KR20200104368A (en) * 2017-12-29 2020-09-03 디에스엠 아이피 어셋츠 비.브이. Compositions and articles for additive manufacturing, and methods of using the same
KR102239212B1 (en) * 2018-12-14 2021-04-12 주식회사 엘지화학 Photopolymer composition
WO2020122678A1 (en) * 2018-12-14 2020-06-18 주식회사 엘지화학 Photopolymer composition
EP3772671A1 (en) 2019-08-06 2021-02-10 Covestro Deutschland AG Layer structure for the light exposure of holograms
ES2963992T3 (en) * 2021-02-11 2024-04-03 Xetos Ag 2K system
WO2023156482A1 (en) 2022-02-21 2023-08-24 Covestro Deutschland Ag Thermostable photopolymers in the visible spectral range and photopolymer compositions containing same
WO2023156484A1 (en) 2022-02-21 2023-08-24 Covestro Deutschland Ag Photopolymer compositions for thermostable photopolymers in the visible spectral range
WO2024052256A1 (en) 2022-09-07 2024-03-14 Covestro Deutschland Ag Specific benzopyrylium salts as dyestuffs for photopolymer compositions

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933682A (en) * 1973-01-31 1976-01-20 Sun Chemical Corporation Photopolymerization co-initiator systems
US4113592A (en) * 1975-04-14 1978-09-12 Celanese Corporation Trihalogenated hydrocarbons as co-photoinitiators
DE2759164A1 (en) * 1977-12-31 1979-07-12 Basf Ag PHOTOPOLYMERIZABLE COATING AND RECORDING MATERIALS CONTAINING A PHOTOINITIATOR AND AN ORGANIC HALOGEN COMPOUND
DE3004694A1 (en) * 1980-02-08 1981-08-13 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING AROMATICALLY BONDED SULFOCHLORIDE GROUPS WITH AROMATIC ISOCYANATES
AU566310B2 (en) * 1983-06-27 1987-10-15 Stauffer Chemical Company Photopolymerizable composition
DE3677527D1 (en) 1985-11-20 1991-03-21 Mead Corp IONIC COLORS AS PHOTOSENSITIVE MATERIALS CONTAINING INITIATORS.
JPH01229003A (en) * 1988-03-09 1989-09-12 Fuji Photo Film Co Ltd Photo-polymerizable composition
JPH0820733B2 (en) * 1988-08-11 1996-03-04 富士写真フイルム株式会社 Photopolymerizable composition for dry film resist
JPH02149849A (en) * 1988-11-30 1990-06-08 Oki Electric Ind Co Ltd Photosensitive resin composition
JPH02275956A (en) * 1988-12-23 1990-11-09 Oki Electric Ind Co Ltd Photoresist composition
JP2861253B2 (en) * 1990-05-15 1999-02-24 ソニー株式会社 Photosensitive resin composition
JPH04107560A (en) * 1990-08-29 1992-04-09 Mitsubishi Kasei Corp Negative type photosensitive composition
US5286600A (en) * 1991-08-27 1994-02-15 Mitsubishi Kasei Corporation Negative photosensitive composition and method for forming a resist pattern by means thereof
JPH09179305A (en) * 1995-12-27 1997-07-11 Toshiba Corp Photosensitive composition, pattern formation and formation of colored film
JP3441246B2 (en) * 1995-06-07 2003-08-25 富士写真フイルム株式会社 Photopolymerizable composition
JPH1068814A (en) * 1996-08-26 1998-03-10 Chisso Corp Color filter forming material
JP2001527565A (en) * 1997-05-23 2001-12-25 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド Polyborate coinitiator for photopolymerization
US6482551B1 (en) * 1998-03-24 2002-11-19 Inphase Technologies Optical article and process for forming article
US6646088B2 (en) * 2000-08-16 2003-11-11 3M Innovative Properties Company Urethane-based stain-release coatings
KR100719426B1 (en) * 2000-08-29 2007-05-18 제이에스알 가부시끼가이샤 Composition Having Refractive Index Sensitively Changeable by Radiation and Method for Forming Refractive Index Pattern
JP3992550B2 (en) * 2002-07-04 2007-10-17 國宏 市村 Active energy ray resin composition, active energy ray resin film, and pattern forming method using the film
KR20060122928A (en) * 2004-02-13 2006-11-30 도아고세이가부시키가이샤 Volume hologram recording material and volume hologram recording medium
EP1746469A1 (en) * 2004-05-10 2007-01-24 Konica Minolta Medical & Graphic Inc. Holographic recording medium, holographic recording method, and holographic information medium
KR101411346B1 (en) * 2004-07-14 2014-06-25 아사히 가세이 이-매터리얼즈 가부시키가이샤 Photosensitive composition, pattern forming material, photosensitive laminate, pattern forming apparatus and method of pattern formation
JP2007066404A (en) * 2005-08-30 2007-03-15 Fujifilm Corp Optical recording method, optical recording apparatus, optical recording medium, and optical recording and reproducing method
JP5130230B2 (en) * 2007-02-05 2013-01-30 新日鉄住金化学株式会社 Volume phase hologram recording material and optical information recording medium
EP2137732B1 (en) 2007-04-11 2012-07-25 Bayer MaterialScience AG Advantageous recording media for holographic applications
JP2008275671A (en) * 2007-04-25 2008-11-13 Fujifilm Corp Holographic recording composition, holographic recording medium, information recording method, and acid generation accelerator
US20100011672A1 (en) * 2008-07-16 2010-01-21 Kincaid Don H Coated abrasive article and method of making and using the same
IL200996A0 (en) * 2008-10-01 2010-06-30 Bayer Materialscience Ag Photopolymer formulations having a low crosslinking density
JP5792746B2 (en) * 2010-02-02 2015-10-14 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ Photosensitive polymer composition containing ester-based writing monomer
WO2011095441A1 (en) * 2010-02-02 2011-08-11 Bayer Materialscience Ag Photopolymer formulation having triazine-based writing monomers
EP2450893A1 (en) * 2010-11-08 2012-05-09 Bayer MaterialScience AG Photopolymer formula for producing of holographic media with highly networked matrix polymers
JP5998722B2 (en) * 2011-08-03 2016-09-28 三菱化学株式会社 Composition for hologram recording medium and hologram recording medium using the same
JP2014535071A (en) 2011-10-12 2014-12-25 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ Sulfur-containing chain transfer agents in polyurethane-based photopolymer formulations

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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